Rheology modifiers

ABSTRACT

Polysaccharide alkali swellable rheology modifiers include an emulsion polymer including at least one polysaccharide portion and at least one synthetic portion wherein the at least one synthetic portion is obtained from at least one anionic ethylenically unsaturated monomer, at least one nonionic ethylenically unsaturated monomer or a combination thereof; wherein at least one of the nonionic ethylenically unsaturated monomers is a hydrophobic ethylenically unsaturated monomer, as well as methods of making polysaccharide alkali swellable rheology modifiers.

This application is a national stage filing under 35 U.S.C. §371 ofPCT/EP2014/054515, filed Mar. 10, 2014, which claims priority to U.S.Provisional Patent Application No. 61/778,584, filed Mar. 13, 2013, andEuropean Patent Application No. 13175109.1, filed Jul. 4, 2013, thecontents of which are each incorporated herein by reference in theirentireties.

FIELD OF THE INVENTION

The present invention relates to rheology modifiers. More specifically,the present invention relates to polysaccharide alkali swellablerheology modifiers.

BACKGROUND

Rheology modifiers are used in a variety of personal care and industrialapplications. Most of the conventional rheology modifiers are producedfrom petrochemical based raw materials. Accordingly, there is a need toproduce rheology modifiers that are at least partly derived fromrenewable raw materials.

One of the benefits of rheology modifiers is their ability to suspendsolid materials in aqueous systems. Suspension benefits are usuallyobtained by using crosslinked polyacrylic acids, such as carbomer-typepolymers. These crosslinked polyacrylic acid-based materials areconventionally made in a solvent and therefore are not consideredenvironmentally friendly, or “green”. Accordingly, there is a need toprovide more environmentally, or “greener”, rheology modifiers and inparticular such rheology modifiers that can deliver suspension benefitsto a variety of formulations.

SUMMARY OF THE INVENTION

In an aspect, the invention is directed to a polysaccharide alkaliswellable rheology modifier comprising an emulsion polymer comprising atleast one polysaccharide portion and at least one synthetic portion. Thesynthetic portion is obtained from at least one anionic ethylenicallyunsaturated monomer and at least one nonionic ethylenically unsaturatedmonomer. At least one of the nonionic ethylenically unsaturated monomersis a hydrophobic ethylenically unsaturated monomer.

In another aspect, the invention is directed to a method of making apolysaccharide alkali swellable rheology modifier. The method comprisesemulsion polymerizing a polysaccharide, at least one anionicethylenically unsaturated monomer and at least one nonionicethylenically unsaturated monomer in the presence of an initiatingsystem. At least one of the nonionic ethylencially unsaturated monomersis a hydrophobic ethylenically unsaturated monomer. The hydrophobicethylenically unsaturated monomer is present in an amount effective toform an emulsion.

BRIEF DESCRIPTION OF THE DRAWING

The invention is best understood from the following detailed descriptionwhen read in connection with the accompanying drawings. Included in thedrawings are the following figures:

FIG. 1 is an example of a flow curve used in calculating zero-shearobtained by plotting viscosity versus shear rate of the specifiedsamples.

FIG. 2 is a comparison of two photographs showing a base shampoo sampleprepared with the polymer according to Example 1 compared to the samebase shampoo sample but without the polymer according to Example 1.

DETAILED DESCRIPTION OF THE INVENTION

The invention generally relates to rheology modifiers that are alkaliswellable. For purposes of the present invention, “polysaccharide alkaliswellable rheology modifier” means that the polysaccharide alkaliswellable rheology modifier is alkali swellable. In an aspect, thepolysaccharide alkali swellable rheology modifier comprises apolysaccharide portion and a synthetic portion obtained from an anionicethylenically unsaturated monomer, a hydrophobic ethylenicallyunsaturated monomer and, optionally, an associative monomer. When theassociative monomer is used the resulting polymer is defined as a“polysaccharide hydrophobically modified alkali swellable rheologymodifier”. Polysaccharide alkali swellable rheology modifiers contain apolysaccharide portion modified by select synthetic monomers where theresulting product delivers rheology modification to aqueous systems.

For purposes of the present invention, “polysaccharide alkali swellablerheology modifier composition” means that the polysaccharide alkaliswellable rheology modifier composition comprises a polysaccharidealkali swellable rheology modifier comprising of polysaccharide portionand a synthetic portion obtained from an anionic ethylenicallyunsaturated monomer, a hydrophobic ethylenically unsaturated monomerand, optionally, an associative monomer, unreacted polysaccharide andwater.

In an embodiment, the invention relates to a polysaccharide alkaliswellable rheology modifier and its use in personal care, fabric andcleaning, oil field, agricultural, paint and coating and otherindustrial applications. The personal care applications include, but arenot limited to, formulations for hair styling gels, skin creams, sun tanlotions, moisturizers, tooth pastes, medical and first aid ointments,cosmetic ointments, suppositories, cleansers, lipstick, mascara, hairdye, cream rinse, shampoos, body soap and deodorants.

Some non-limiting examples of industrial applications for the polymersof this invention are caulk, sealants, mortars, paints and coatings,papermaking, paper coatings, adhesives, oil field additives, grouts,soaps, detergents and fabric care applications.

Suitable polysaccharides useful in the present invention can be derivedfrom plant, animal and microbial sources and are preferably watersoluble at the temperatures at which the polymerization reaction iscarried out. For purposes of this invention, the term “water soluble”means that the polysaccharide has about 0.1% or greater solubility inwater at reaction temperature, preferably about 1% or greater solubilityin water at reaction temperature, and more preferably about 5% orgreater solubility in water at reaction temperature. The reactiontemperatures can vary depending on the initiating system and thepressure that the reaction is under. In an embodiment, the reactiontemperature range can be about 25 to about 150° C., in anotherembodiment about 30 to about 120° C., but typically the reactions areconducted in the temperature range of about 40 to about 100° C.

Examples of such polysaccharides include starch, cellulose, gums (e.g.,gum arabic, guar and xanthan), alginates, pectin, chitin, chitosan,carrageenan, inulin and gellan. Starches include those derived frommaize and conventional hybrids of maize, such as waxy maize and highamylose (greater than 40% amylose) maize, as well as other starches suchas potato, tapioca, wheat, rice, pea, sago, oat, barley, rye, andamaranth, including conventional hybrids or genetically engineeredmaterials. In an embodiment, the preferred polysaccharide is starch and,in an embodiment, the preferred starch is based on potato. The starchescan be of the native variety or a hybrid variety produced by traditionalbreeding programs or by artificial gene manipulation. These hybridsinclude, but not limited to waxy versions (starches with little or noamylose) and high amylose cultivars. Waxy starches are typically definedas having about 5% or less amylose and sometime containing about 2% orless amylose. In an embodiment, the waxy starches have about 95% orgreater amylopectin. High amylose starches are defined as having about40% or greater amylose (with the exception of pea starch which has ahigh amylose content of about 27% or greater amylose). In a furtherembodiment, the high amylose starches have an amylose content of about60% or greater amylose. In addition, starches which have altered chainlength and branch points are included in this application. In anembodiment, the preferred polysaccharides are starches or cellulosesand/or their derivatives.

In an embodiment of the invention, the polysaccharides are starches andstarch derivatives, including, but not limited, to thermal and/ormechanically treated starch, oxidatively, hydrolytically orenzymatically degraded starches, and chemically modified starches. Theseinclude maltodextrins, dextrin, pyrodextrins, oxidized starches,cyclodextrins and substituted cyclodextrins and higher molecular weightstarches or derivatives thereof. Starch and starch hydrolyslates thatare hydrogenated are preferred since they lead to low color in the finalapplication especially those that are in the alkaline pH range. Chemicalmodification includes hydrolysis by the action of acids, enzymes,oxidizers or heat, esterification or etherification. The chemicallymodified starches, after undergoing chemical modification may becationic, anionic, non-ionic or amphoteric or hydrophobically modifiedand maybe crosslinked.

In one embodiment of the invention, the polysaccharides may bepregelatinized starches and starch derivatives. The pregelatinizedstarches suitable for use in the present invention are those starchesthat have been treated with heat, moisture, or chemicals to disrupt thenatural granular structure and render the starch soluble in water atbelow the gelatinization temperature of the native starch. For purposesof the invention, pregelatinized starches are also referred to as coldwater soluble starches (CWS) and the terms are used interchangeably. Fora general review of how to prepare pregelatinized starches see (Starch;Chemistry and Technology, R. L. Whistler, second edition, AcademicPress, Inc. New York, 1984 pages 670-673). Additionally these productscan be prepared by co-jet cooking coupled to a spray drier (see Kasicaet al. U.S. Pat. No. 5,571,552). In addition to being pregelatinized,the starches of this invention can further be modified to containanionic, cationic, non-ionic and reactive groups. Derivatives of thesetypes are described in “Modified Starches: Properties and Uses” O. B.Wurzburg, CRC Press Boca Raton, Fla., 1986 chapters 3-9. The modifiedstarches can be prepared in the granular form and then made CWS or canbe reacted in solution to produce the polymers of this invention.However, the starches can be gelatinized or cooked in the initial partof the polymerization process to produce the polysaccharide alkaliswellable rheology modifiers by heating the starch solution at about 60to about 100° C. for a long enough time to effect gelatinization. Thus,non pregelatinized starches and starch derivatives can be used bycooking them in situ.

In an embodiment, polysaccharides suitable for use with the presentinvention also include cellulose and cellulose derivatives, such ascarboxymethyl cellulose (CMC), hydroxethyl cellulose (HEC),carboxymethyl hydroxethyl cellulose (CMHEC), hydroxypropyl cellulose,sulfoethyl cellulose and its derivatives, ethyl hydroxyethyl cellulose(EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobicallymodified ethyl hydroxyethyl celluloses HM-EHEC some of which areavailable from AkzoNobel. Polysaccharides also include cellulosicderivatives including plant heteropolysaccharides commonly known ashemicelluloses which are by products of the paper and pulp industry.Hemicelluloses include xylans, glucuronoxylans, arabinoxylans,glucomannans, and xyloglucans. Xylans are the most commonheteropolysaccharide and are preferred. Polysaccharides such asdegradation products of cellulose such as cellobiose are suitable forpreparing the polymers of this invention. In an embodiment, thepreferred cellulosic materials are Carboxymethyl cellulose (CMC),hydroxethyl cellulose (HEC), carboxymethyl hydroxethyl cellulose(CMHEC), hydroxypropyl cellulose, ethyl hydroxyethyl cellulose (EHEC),methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobicallymodified ethyl hydroxy ethyl celluloses (HM-EHEC). These celluloses ortheir derivatives generally have high viscosity in aqueous solutions dueto their high molecular weight. It is preferable that the viscosity ofthe cellulose solution be low enough to effectively conduct thepolymerization. Lower molecular weight celluloses can be used for thispurpose. Alternatively, higher molecular weight cellulose or itsderivative may be used and depolymerized before or during thepolymerization process. The methods to depolymerize cellulose and itsderivatives are known to those of ordinary skill in the art. In anembodiment, it is preferred that the viscosity of a 1% aqueous solutionof the cellulose or its derivative be less than about 5000 cps, inanother embodiment preferably be less than about 1000 cps and in yetanother embodiment most preferably be less than about 100 cps at 25° C.

In an embodiment, when the polysaccharide is a cellulose, it ispreferred that the cellulose be water soluble. For purposes of thisinvention, a cellulose that is water soluble has, in an embodiment,about 0.1% or greater solubility in water at 25° C. (i.e. the lowestreaction temperature), in another embodiment preferably about 1% orgreater solubility in water at 25° C., and in yet another embodimentmore preferably about 5% or greater solubility in water at 25° C. Waterinsoluble cellulose derivatives such as viscose, rayon, celluloseacetate butyrate and others are not suitable for use in the presentinvention since they do not make stable emulsions when used in thepolymerization process of this invention.

Other suitable polysaccharides include guar, unwashed guar gum, washedguar gum, cationic guar, carboxymethyl guar (CM guar), hydroxyethyl guar(HE guar), hydroxypropyl guar (HP guar), carboxymethylhydroxypropyl guar(CMHP guar), hydrophobically modified guar (HM guar), hydrophobicallymodified carboxymethyl guar (HMCM guar), hydrophobically modifiedhydroxyethyl guar (HMHE guar), hydrophobically modified hydroxypropylguar (HMHP guar), cationic hydrophobically modified hydroxypropyl guar(cationic HMHP guar), hydrophobically modifiedcarboxymethylhydroxypropyl guar (HMCMHP guar), hydrophobically modifiedcationic guar (HM cationic guar), guar hydroxypropyl triammoniumchloride, hydroxypropyl guar hydroxypropyl triammonium chloride.Polysaccharides may also include inulin and its derivatives, such ascarboxymethyl inulin. These guars or its derivatives generally have highviscosity in aqueous solutions due to their high molecular weight. It ispreferable that the viscosity of the guar solution be low enough toeffectively conduct the polymerization. Lower molecular weight guars canbe used for this purpose. Alternatively, higher molecular weight guar orits derivative may be used and depolymerized before or during thepolymerization process. The methods to depolymerize polysacharides andits derivatives are well known to those of ordinary skill in the art. Inan embodiment, it is preferred that the viscosity of a 1% aqueoussolution of the guar or its derivative be less than about 5000 cps, inanother embodiment preferably be less than 1000 cps and in yet anotherembodiment most preferably be less than 100 cps at 25° C.

In an embodiment, the minimum weight percent of the polysaccharides foruse with the present invention are in the range of about 5% of thepolysaccharide alkali swellable rheology modifier, preferably in therange of about 10% of the polysaccharide alkali swellable rheologymodifier, and most preferably in the range of about 15% of thepolysaccharide alkali swellable rheology modifier. The weight of thepolysaccharide alkali swellable rheology modifier is the sum of theweight of the polysaccharide and the synthetic monomers that make upthis polymer. In an embodiment, the maximum weight percent of thepolysaccharide is in the range of about 90% of the polysaccharide alkaliswellable rheology modifier, in another embodiment preferably in therange of about 75% of the polysaccharide alkali swellable rheologymodifier, and in yet another embodiment most preferably in the range ofabout 60% of the polysaccharide alkali swellable rheology modifier.

In an embodiment, the weight average molecular weight of thepolysaccharide is preferably about 5,000,000 or less, in anotherembodiment more preferably about 1,000,000 or less, and in yet anotherembodiment most preferably about 500,000 or less. These polysaccharidesmay be further depolymerized as necessary for stability of the emulsionand rheology modification performance.

The molecular weight of the water soluble polysaccharides of the presentinvention can be determined using gel permeation chromatography (GPC)with Viscotech Triple Detector Array using the method below:

-   -   Eluent: 0.03M NaNO3 in DMSO.    -   Columns: 1 Phenogel MXM 7.8 mm×300 mm GPC column from        Phenomenex. 40° C.    -   Flow Rate: 0.8 ml/min    -   Detector: Viscotech TDA Model 302 Triple Detector Array    -   Pump/Autosampler: Agilent Model 1100    -   Primary Standard: Pullulan 100,000 MW from American Polymer        Standards.    -   Sample The samples were prepared by dissolving the samples in        0.03M    -   Preparation: NaNO3 in DMSO at 90 C for 1 hour. Concentration was        about 2.0 mg/ml.    -   Injection Volume: 100 μl for the standard and samples.    -   Software: Visocotech Omnisec Software using the universal        calibration method.

When the polysaccharide is a starch, the molecular weight can bemeasured in terms of water fluidity. Starch water fluidity (‘WF’) ismeasured using a Thomas Rotational Shear-Type Viscometer (manufacturedby Arthur H. Thomas Co., Philadelphia, Pa. 19106), standardized at 30°C. with a standard oil having a viscosity of 24.73 mPas, requiring23.12+/−0.05 seconds for 100 revolutions. Accurate and reproduciblemeasurements of WF are obtained by determining the time which elapsesfor 100 revolutions at different solids levels depending on the starch'sdegree of conversion (as the degree of conversion increases, WFincreases and viscosity decreases). The procedure used involvesslurrying the required amount of starch (e.g., 6.16 g, dry basis) in 100ml of distilled water in a covered copper cup and heating the slurry ina boiling water bath for 30 minutes with occasional stirring. The starchdispersion is then brought to the final weight (e.g., 107 g) withdistilled water. The time required for 100 revolutions of the resultantdispersion at 81-83° C. is recorded and converted to a water fluiditynumber using the following conversion Table 1:

TABLE 1 Time Required for 100 Revolutions (seconds) Amount of Starchused (anhydrous, g) 6.16^(a) 8.80^(b) 11.44^(c) 13.20^(d) Water Fluidity60.0 5 39.6 10 29.3 15 22.6 20 20.2 25 33.4 30 27.4 35 22.5 40 32.5 4526.8 50 22.0 55 24.2 60 19.2 65 15.9 70 13.5 75 11.5 80 10.0 85 9.0 90For ^(a), ^(b), ^(c) and ^(d), final weight of each starch solution is107, 110, 113 and 115 g, respectively.

Prior work has determined the correlation between the molecular weightof fluidity starches (measured by light scattering methods) and theirWF, as shown in Table 2.

TABLE 2 Molecular weight vs. WF for degraded corn starch Sample # WF Mw× 10⁶ 1 39 93.5 2 45.2 75.5 3 66.1 15.4 4 73.0 6.42

In an embodiment, the water fluidity of the starch is preferably about75 or higher, in another embodiment more preferably about 80 or higher,and in yet another embodiment most preferably about 85 or higher.

The polymers of this invention form emulsion compositions or aqueousemulsion paste compositions which can be used as is or dried. Stableemulsions are typically formed with lower molecular weightpolysaccharides. However, the higher molecular weight polysaccharidesthat may form an aqueous emulsion paste may give better rheologyproperties. In an embodiment of this invention, the polymers do not formcrosslinked gels compositions during the reaction. These crosslinkedgels cannot be diluted in water and neutralized to give rheologymodification to aqueous systems.

If an aqueous emulsion paste is formed, the aqueous emulsion paste canbe converted to a stable emulsion by a number of post treatmentprocesses. These include, enzyme treatment or addition of a rheologymodifier that is capable of suspending the particles of the aqueousemulsion paste. In an embodiment, the particle size in these emulsionsor aqueous emulsion pastes that may be substantially free of surfactantsare preferably about 2000 nm or less, in another embodiment morepreferably about 1000 nm or less and in yet another embodiment mostpreferably about 500 nm or less. In an embodiment, the residual monomerof each of the monomers in these emulsions or aqueous emulsion pastesthat are substantially free of surfactants are preferably about 1000 ppmor less, in another embodiment more preferably about 500 ppm or less andin yet another embodiment most preferably about 250 ppm or less.

In an embodiment, the invention relates to a polysaccharide alkaliswellable rheology modifier composition. The composition comprises apolysaccharide alkali swellable rheology modifier comprising apolysaccharide portion and a synthetic portion obtained from an anionicethylenically unsaturated monomer and at least one nonionicethylenically unsaturated monomer, At least one of the nonionicethylenically unsaturated monomers is a hydrophobic ethylenicallyunsaturated monomer present in a high enough amount to force the polymerinto an emulsion form. Optionally, the polysaccharide alkali swellablerheology modifier composition may also include an associative monomer,unreacted polysaccharide and water. This can be in the form of a stableemulsion (e.g. a stable emulsion composition) or in the form of anaqueous emulsion paste (e.g. an aqueous emulsion paste composition).

In an embodiment of the invention, the emulsion polymers areself-stabilizing and unlike regular emulsion polymers may besubstantially free of surfactants, such as stabilizing surfactants,during the polymerization process. The polymers of this invention do notform solution polymers wherein the polymer is completely soluble in thesolvent, water. In emulsion polymers, the polymer is in the form ofparticles which are stabilized (but not soluble) in water at the acidicpH of the system. In typical cases, the pH is in the range 2 to 6 andmore typically in the range 2.5 to 5.5. For purposes of this invention,in an embodiment, substantially free of surfactants means that thepolymers have about 0.1 wt % or less surfactant, in another embodiment,about 0.01 wt % or less surfactant by weight of the polysaccharide andmonomers and in yet another embodiment no surfactant is present duringthe polymerization process. By polymerizing under conditions thatminimize the amount of surfactants present, the chances of the monomersreacting with the polysaccharide to form the polysaccharide alkaliswellable rheology modifier is increased. In an embodiment of theinvention, a stabilizing surfactant may be added after thepolymerization to stabilize the emulsion composition.

As used herein, the term “anionic ethylenically unsaturated monomer”means an ethylenically unsaturated monomer which is capable ofdeveloping a negative charge when the polysaccharide alkali swellablerheology modifier is in an aqueous solution. These anionic ethylenicallyunsaturated monomers can include, but are not limited to, acrylic acid,methacrylic acid, ethacrylic acid, α-chloro-acrylic acid, α-cyanoacrylic acid, β-methyl-acrylic acid (crotonic acid), α-phenyl acrylicacid, β-acryloxy propionic acid, sorbic acid, α-chloro sorbic acid,angelic acid, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylicacid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid,citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaricacid, tricarboxy ethylene, muconic acid, 2-acryloxypropionic acid,2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodiummethallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid,vinyl phosphonic acid and maleic acid. Combinations of anionicethylenically unsaturated monomers can also be used. In an embodiment ofthe invention, the anionic ethylenically unsaturated monomer maypreferably be methacrylic acid, maleic acid, acrylic acid, itaconicacid, 2-acrylamido-2-methyl propane sulfonic acid or mixtures thereof.In an embodiment, most preferably the anionic ethylenically unsaturatedmonomer is methacrylic acid or acrylic acid, or combinations thereof.

As used herein, the term “nonionic ethylenically unsaturated monomer”means an ethylenically unsaturated monomer which does not introduce acharge in to the polymers of this invention. These nonionicethylenically unsaturated monomers include, but are not limited to,acrylamide, methacrylamide, N alkyl(meth)acrylamide, N,Ndialkyl(meth)acrylamide such as N,N dimethylacrylamide,hydroxyalkyl(meth)acrylates, alkyl(meth)acrylates such as methylacrylateand methylmethacrylate, vinyl morpholine, vinyl pyrrolidone, vinylcaprolactum, ethoxylated alkyl, alkaryl or aryl monomers such asmethoxypolyethylene glycol (meth)acrylate, allyl glycidyl ether, allylalcohol, glycerol (meth)acrylate, and others.

For purposes of the present invention, the term “hydrophobicethylenically unsaturated monomer” means a monomer that is hydrophobicand results in the formation of an emulsion system when reacted with thepolysaccharide and the anionic ethylenically unsaturated monomer. Forpurposes of this invention, a hydrophobic monomer is a nonionicethylenically unsaturated monomer defined as any nonionic ethylenicallyunsaturated monomer having a water solubility of less than 3 grams per100 mls of water at 25° C. and preferably less than 1 gram per 100 mlsof water at 25° C. and most preferably less than 0.1 gram per 100 mls ofwater at 25° C. These hydrophobic monomers may contain linear orbranched alk(en)yl, cycloalkyl, aryl, alk(en)aryl moieties. Suitablehydrophobic ethylenically unsaturated monomers include C1-C7 alkylesters or amides of acrylic and methacrylic acid including ethyl(meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, styrene,vinyltoluene, t-butyl styrene, isopropylstyrene, and p-chlorostyrene;vinyl acetate, vinyl butyrate, vinyl caprolate, acrylonitrile,methacrylonitrile, butadiene, isobutylene, isoprene, vinyl chloride,vinylidene chloride, tertiary butyl acrylamide, benzyl (meth)acrylate,phenyl (meth)acrylate, benzyl ethoxylate (meth)acrylate, phenylethoxylate (meth)acrylate, 2-ethylhexyl(meth)acrylate,2-butyloctyl(meth)acrylate, 2-hexyldecyl(meth)acrylate,2-octyldodecyl(meth)acrylate, 2-decyltetradecyl(meth)acrylate,2-dodecylhexadecyl(meth)acrylate, isopropyl(meth)acrylate,isobutyl(meth)acrylate, tertiary butyl (meth)acrylate, t-octylacrylamide, octyl acrylate, lauryl acrylate, stearyl acrylate, behenylacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, laurylmethacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexylacrylamide, n-octyl acrylamide, lauryl acrylamide, stearyl acrylamide,behenyl acrylamide, propyl acrylate, butyl acrylate, pentyl acrylate,hexyl acrylate, 1-allyl naphthalene, 2-allyl naphthalene, 1-vinylnaphthalene, 2-vinyl naphthalene, monomers containing silane, silanoland siloxane functionalities. Combinations of the above hydrophobicethylenically unsaturated monomers may also be used. Preferred are ethyl(meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl acrylate, butyl(meth)acrylate, vinyl acetate, tertiary butyl acrylamide andcombinations thereof. In an embodiment, ethyl acrylate, methyl acrylate,vinyl acetate, butyl acrylate and combinations thereof are preferred.

For purposes of the present invention, an associative monomer isintended to mean an ethylenically unsaturated monomer containing ahydrophobe and a spacer moiety which allows the hydrophobe to besufficiently far away from the backbone of the polymer to formhydrophobic associations in aqueous solutions. The spacer moieties areusually ethoxylate groups but any other group that extends thehydrophobe away from the backbone of the polymer may be used. Thehydrophobes with a spacer moiety include, but are not limited to,alcohol ethoxylates, alkylphenoxy ethoxylates, propoxylated/butoxylatedethoxylates, ethoxylated silicones and the like. In an embodiment, thepreferred hydrophobes with spacer moieties include alcohol ethoxylatesand/or alkylphenoxy ethoxylates. In another embodiment, alcoholethoxylates containing alcohols with carbon chain lengths of 6 to 40 and6 to 100 moles of ethoxylation are more preferred. In yet anotherembodiment, alcohol ethoxylates containing alcohols with carbon chainlengths of 12 to 22 and 15 to 30 moles of ethoxylation are particularlypreferred. The hydrophobes may be linear or branched alk(en)yl,cycloalkyl, aryl, alk(en)aryl or an alkoxylated derivative. In anembodiment, the most preferred hydrophobes are linear or branchedalcohols and amines containing 12 to 32 carbons. The associative monomermay contain an ethylenically unsaturated monomer covalently linked tothe hydrophobe. In an embodiment, the ethylenically unsaturated monomerpart of the associate monomer preferably is a (meth)acrylate, itaconateand/or maleate which contains ester linking groups. However, theassociative monomer may also contain amide, urea, urethane, ether,alkyl, aryl and other suitable linking groups. The hydrophobe may be analkylamine or dialkylamine ethoxylate. In an embodiment, the(meth)acrylate group is most preferred. In another embodiment, preferredassociative monomers are C₁₂₋₃₂(EO)₁₀₋₃₀ meth(acrylates) orC₁₂₋₃₂(EO)₁₀₋₃₀ itaconates or or C₁₂₋₃₂(EO)₁₀₋₃₀ maleates. Theseassociative monomers are known to those skilled in the art and any ofthe known associative monomers can be used as part of this invention.

In an embodiment, the minimum weight of the anionic ethylenicallyunsaturated monomer is about 15 weight percent or more of the totalmonomer added to the polymerization process, in another embodimentpreferably about 20 weight percent or more of the total monomer added tothe polymerization process, and in yet another embodiment, mostpreferably about 30 weight percent or more of the total monomer added into the polymerization process. In an embodiment, the maximum weight ofthe anionic ethylenically unsaturated monomer is about 80 weight percentor less of the total monomer added in to the polymerization process, ispreferably about 70 weight percent or less of the total monomer added tothe polymerization process, and in another embodiment most preferablyabout 60 weight percent or less of the total monomer added in to thepolymerization process.

In an embodiment according to the present invention, the minimum amountof hydrophobic ethylenically unsaturated monomer required is an amounteffective to form an emulsion, which may depend on the hydrophobicity ofthe monomer. That is, the higher the hydrophobicity the less monomerwould be required to form an emulsion. In an embodiment, the minimumweight of the hydrophobic ethylenically unsaturated monomer effective toform an emulsion is about 10 weight percent or more of the total monomeradded to the polymerization process, in another embodiment preferablyabout 25 weight percent or more of the total monomer added to thepolymerization process, and in yet another embodiment most preferablyabout 40 weight percent or more of the total monomer added to thepolymerization process. In an embodiment, the maximum weight of thehydrophobic ethylenically unsaturated monomer is about 95 weight percentor less of the total monomer added to the polymerization process, inanother embodiment preferably about 90 weight percent or less of thetotal monomer added to the polymerization process, and in yet anotherembodiment most preferably about 80 weight percent or less of the totalmonomer added to the polymerization process.

In an embodiment, the minimum weight of the associative monomer is about0.1 weight percent or more of the total monomer added to thepolymerization process, in another embodiment preferably about 1 weightpercent or more of the total monomer added to the polymerizationprocess, and in yet another embodiment most preferably about 2 weightpercent or more of the total monomer added to the polymerizationprocess. In an embodiment, the maximum weight of the associative monomeris about 30 weight percent or less of the total monomer added to thepolymerization process, in another embodiment preferably about 25 weightpercent or less of the total monomer added to the polymerizationprocess, and in yet another embodiment most preferably about 20 weightpercent or less of the total monomer added in to the polymerizationprocess.

It has been found that styrene or substituted styrene do not react wellwith the polymers of the invention and may lead to high residual monomerlevels which cause undesirable odors. Accordingly, in an embodiment ofthe invention, if styrene or substituted styrene is included as one partof the hydrophobic ethylenically unsaturated monomer, then the amount ofthis monomer is preferably about 10 weight percent or less of the totalmonomer, in another embodiment more preferably about 5 weight percent orless of the total monomer and in yet another embodiment is mostpreferably about 1 weight percent or less of the total monomer.

In an aspect, the present invention is directed to a process forpreparing the polysaccharide alkali swellable rheology modifiers. Theprocess comprises dissolving the polysaccharide in water and heating thesolution to a temperature sufficient to initiate the reaction. In anembodiment, the temperature sufficient to initiate the reaction isapproximately 25 to 150° C. and in another embodiment preferably 30° C.to 95° C. In an embodiment, the polysaccharide maybe depolymerizedbefore or during the polymerization step to a molecular weight that issufficient to provide a stable emulsion in the end product. In anembodiment, the depolymerization may be accomplished by using freeradicals or enzymes or any other process known to those of ordinaryskill in the art. In a typical process according to the presentinvention, a mixture of monomers and an aqueous solution of an initiatorare added over a period of time. In an embodiment, the monomer may bemethacrylic acid mixed with a hydrophobic monomer, such as ethylacrylate. Optionally, an associative monomer maybe added to the monomermix. After the polymerization is completed, the reaction mixture is thencooked for a period of time sufficient to lower the residual monomer.Additional initiator to scavenge any remaining monomer may then beadded. The temperature required depends on the initiating system usedand would be known to one skilled in the art. The residual level of eachmonomer is less than about 1000 ppm of the emulsion polymer composition,more preferably less than about 500 ppm of the emulsion polymercomposition, and most preferably less than about 100 ppm of the emulsionpolymer composition.

In an embodiment, chain transfer agents and crosslinking agents may beadded during the polymerization process. Suitable chain transfer agentsinclude, but are not limited to, mercaptans, such as, for example,dodecylmercaptan, methyl mercaptopropionate, and 3-mercaptopropionicacid, 2-mercaptoethanol, combinations thereof and the like.

Suitable crosslinking agents include, but are not limited to,polyethylenically unsaturated copolymerizable monomers that typicallyhave 2 or more double bonds which are effective for crosslinking, suchas, for example, diallylphthalate, divinylbenzene, vinyl crotonate,allyl methacrylate, trimethylol propane triacrylate, ethylene glycoldiacrylate or dimethacrylate, polyethylene glycol diacrylate ordimethacrylate, 1,6-hexanediol diacrylate or dimethacrylate, diallylbenzene, combinations thereof, and the like.

The resulting reaction product may be in one or more forms. In anembodiment, the reaction product may be in the form of a stable emulsioncomposition containing water, the polymers of the invention and anyunreacted polysaccharide which is a liquid and then ready to use bydiluting to the necessary concentration and adding a neutralizationagent. In another embodiment, the reaction product may be in the form ofan aqueous emulsion paste composition that contains water. For purposesof this invention, an “aqueous emulsion paste composition” is defined asan emulsion containing water, the polymers of the invention and anyunreacted polysaccharide that does not flow like a liquid, but insteadhas solid like flow properties. Once the paste is formed and separatedfrom the reaction product, the aqueous emulsion paste is stable as asolid containing water with in an embodiment about 10 weight % or more,in another embodiment preferably about 15 weight % or more and in yetanother embodiment most preferably about 20 weight % or more solids, andthe emulsion does not phase separate for approximately 1 month at 25° C.In another embodiment, the emulsion does not separate for approximately6 months at 25° C. This aqueous emulsion paste maybe used as is, but forease of handling, the aqueous emulsion paste composition may be driedand the dried product may be used. In a further embodiment, astabilizing agent may be added to the aqueous emulsion paste composition(post polymerization) to form a stable emulsion composition which thencan be used. This stabilizing agent may be a synthetic or a naturallyderived polymeric thickener or gelling additive. Some examples of suchmaterials include, but are not limited to, pectin, alginate, xanthangum, guar, cellulosics and chemically or physically modified derivativesof these natural polymeric thickeners, such as carboxymethyl cellulose,hydroxyethyl cellulose, hydroxyethyl ethylcellulose, hydroxypropylcellulose, oxidized cellulose and dehydro-xanthan gum. In an embodiment,the preferred stabilizing agent is guar, xanthan or a cellulosederivative, such as ethyl hydroxyethyl cellulose (EHEC). In anembodiment, the stabilizing agent is about 1 weight percent or more ofthe polymer of the emulsion paste composition but can be as high asabout 5 to about 20 weight percent of the polymer of the emulsion pastecomposition.

For purposes of this invention, a stable emulsion system is defined ascomprising the polymers of this invention, unreacted polysaccharide andwater, in liquid form, with at about 10 weight % or more and preferablyabout 15 weight % or more and most preferably about 20 weight % or moresolids, and in an embodiment the emulsion does not phase separate forapproximately 1 month at 25° C. and in another embodiment preferablydoes not separate for approximately 6 months at 25° C.

The stable emulsion composition or the aqueous emulsion pastecomposition may be diluted with water and then neutralized to giveviscosity and rheology to the aqueous systems. In one embodiment of theinvention, the stable emulsion composition or the aqueous emulsion pastecomposition is readily dilutable. For purposes of this invention,“readily dilutable” means that the emulsion composition or the aqueousemulsion paste composition can be diluted to about a 1-5 weight %,aqueous polymer solution or dispersion by adding water using stirringand adding a neutralizing agent and heating, if necessary, and morepreferably diluted to about a 1-5 weight % aqueous polymer solution ordispersion by adding water and using stirring. After the neutralizationagent is added and the pH raised, in an embodiment a pH in the rangefrom about 5 to about 12, in another embodiment from about 5 to about 10and yet another embodiment from about 7 to about 10, the polymer isdissolved in water and forms a solution, i.e. it is no longer in thedispersed or emulsion phase. This is evidenced by a visual change of awhite emulsion to a clear solution. In an embodiment of the invention,the stable emulsion composition or the aqueous emulsion pastecomposition, when diluted to about 2% solids and neutralized to a pH ofabout 8 with suitable neutralizing agents, generates a viscosity at 25°C. of about 500 cps or more, in another embodiment preferably about 2500cps or more and in another embodiment more preferably about 5000 cps ormore at 10 rpm when measured using a Brookfield viscometer.

In an embodiment, the polysaccharide alkali swellable rheology modifieror polysaccharide hydrophobically modified alkali swellable rheologymodifiers include emulsion compositions or aqueous emulsion pastecompositions in the pH range about 2 to about 6. Consequently, thesecompositions need to be activated by neutralizing with a neutralizingagent. Suitable neutralizing agents which may be included in thecomposition of the present invention include, but are not limited to,alkyl monoamines containing from about 2 to about 22 carbon atoms, suchas triethylamine, stearylamine and laurylamine, and amino alcohols suchas triethanolamine, 2-amino-2-methyl-1,3-propanediol and2-amino-2-methyl-1-propanol, and inorganic neutralizing agents, such assodium hydroxide and potassium hydroxide. Other combinations of usefulneutralizing agents are described in U.S. Pat. No. 4,874,604 to Sramek,which is incorporated by reference in its entirety herein. In anembodiment, the neutralizing agents may be used alone or in combination.In an embodiment, the polysaccharide alkali swellable rheology modifieror polysaccharide hydrophobically modified alkali swellable rheologymodifiers are neutralized by a base. The neutralizing agent may bepresent in an amount effective to neutralize a percentage of thepolymer's free acid groups and render the polymer water-soluble orwater-dispersible. In one embodiment, the neutralizing agent may bepresent in an amount sufficient to neutralize the free acid groups ofthe polymer from about 8 percent to about 100 percent neutralization ofthe total free acid groups of the polymer. In another embodiment, thefree acid groups of the polymer may be neutralized from about 25 percentto about 100 percent. In another embodiment, the free acid groups of thepolymer may be neutralized from about 50 percent to about 100 percent.In yet another embodiment, the free acid groups of the polymer will beneutralized from about 70 percent to about 100 percent. In still yetanother embodiment, the free acid groups of the polymer may beneutralized from about 80 to about 100 percent. The base may also beused in excess of 100 percent neutralization to increase the solutionpH. In another embodiment, when the final pH range of the aqueous systemis desired to be about 5 to about 7, the solution containing thepolymers of this invention may be neutralized to the pH of about 7 toabout 9 and then the pH adjusted back to about 5 to about 7 using asuitable acid.

As used herein, the initiating system is any free radical initiatingsystem. In an embodiment, the initiating system is water soluble.Suitable initiators include, but are not limited to, peroxides, azoinitiators as well as redox systems, such as tert-butyl hydroperoxideand erythorbic acid, and metal ion based initiating systems. Initiatorsmay also include both inorganic and organic peroxides. In an embodiment,the inorganic peroxides, such as sodium persulfate, potassium persulfateand ammonium persulfate, are preferred. In a further embodiment, themetal ion based initiating systems including Fe and hydrogen peroxide,as well as Fe in combination with other peroxides, are preferred. Azoinitiators, especially water soluble azo initiators, may also be used.Water soluble azo initiators include, but are not limited to,2,2′-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,2,2′-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate,2,2′-Azobis(2-methylpropionamidine)dihydrochloride,2,2′-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate,2,2′-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride,2,2′-Azobis[2-(2-imidazolin-2-yl)propane],2,2′-Azobis(1-imino-1-pyrrolidino-2-ethylpropane)dihydrochloride,2,2′-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethl]propionamide},2,2′-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and others. Theinitiators when added before the monomer can be used to depolymerize thepolysaccharide to a desired molecular weight. Furthermore, a differentinitiating system could be used during the polymerization process.Finally, a third initiating system can be used to scavenge the residualmonomer. All 3 of these initiating systems can be same of different.Thus, it is contemplated that in an embodiment of the invention,combinations of the initiating systems can also be used.

If persulfate is used in combination with undegraded starch, thepersulfate initiator is preferably about 1 weight percent or less of thetotal weight of the undegraded starch and monomer, and preferably about0.5 weight percent or less of the total weight of the undegraded starchand monomer and most preferably about 0.1 weight percent or less of thetotal weight of the undegraded starch and monomer.

In an embodiment, the invention relates to a polysaccharide alkaliswellable rheology modifier and its use in personal care, fabric andcleaning, oil field, agricultural, adhesive, asphalt emulsions, paintand coatings and other industrial applications. In an embodiment, thepolymers of this invention may be added to these formulations at leastabout 0.1% polymer by weight of the formulation, more preferably atleast about 0.5% polymer by weight of the formulation and mostpreferably at least about 1.0% polymer by weight of the formulation. Inan embodiment, the polymers of this invention may be added to theseformulations at most about 20% polymer by weight of the formulation,more preferably at most about 15% polymer by weight of the formulationand most preferably at least about 10% polymer by weight of theformulation.

The polymers of this invention can be used in aqueous protective coatingcompositions. These polymers increase and maintain the viscosity atrequired levels under specific processing conditions and end-usesituations. In particular, the polymers of this invention are useful inall kinds of coatings such as decorative and protective coatings and inpaper coatings. The polymers of this invention can be used as rheologymodifiers for water-based protective coating compositions. Water-basedprotective coating compositions are commonly known as latex paints ordispersion paints and have been known for a considerable number ofyears. The adjustment of the rheology properties of such an aqueousprotective coating composition is challenging, since the coatingcomposition needs not only to provide good leveling and excellent sagresistance, but rather the coating compositions should also have an ICIviscosity which is neither too low nor too high in order to allow aneasy application.

In agricultural formulations, the polymers of this invention providedrift control of agricultural sprays, reducing carryover to other areasand permitting more efficient spray directly on foliage. The fabric andcleaning applications include use of these polymers in liquiddetergents. These detergent formulations are known in the art andinclude, liquids for fabric cleaning, hard surface cleaners, handdishwash and automatic dishwash.

In oil field applications, the polymers of this invention may be used infracturing operations. For these applications, it is desired to useliquid compositions with viscoelastic properties. Such compositions, forinstance, may be used to stimulate oil wells wherein impeded flow pathslead to an insufficient hydrocarbon production, a technique known as(hydraulic) fracturing and the specialized fluids used in said techniqueare referred to as fracturing fluids. For such a fracturing process, thecompositions are typically injected via the wellbore into the formationat sufficient pressures to create fractures in the formation rocks, thuscreating channels through which the hydrocarbons may more readily flowinto the wellbore. In an embodiment, the fracturing fluids should imparta minimal pressure drop in the pipe within the wellbore during placementand have an adequate viscosity to carry proppant (sand) material thatprevents the fracture from closing. Moreover, the fracturing fluidsshould have a minimal leak-off rate to avoid fluid migration into theformation rocks so that, notably, the fracture can be created andpropagated and should degrade so as not to leave residual material thatmay prevent accurate hydrocarbons to flow into the wellbore.

The personal care applications include, but are not limited to,formulations for hair styling gels, skin creams, sun tan lotions,moisturizers, tooth pastes, medical and first aid ointments, cosmeticointments, suppositories, cleansers, lipstick, mascara, hair dye, creamrinse, shampoos, body soap and deodorants, hair care and stylingformulations, shave prep and hand sanitizers including alcohol basedhand sanitizers.

Suitable personal care applications also include formulation for use onthe skin, eyelashes or eyebrows, including, without limitation, cosmeticcompositions such as mascara, facial foundations, eyeliners, lipsticks,and color products; skin care compositions such as moisturizing lotionsand creams, skin treatment products, skin protection products in theform of an emulsion, liquid, stick, or a gel; sun care compositions suchas sunscreens, sunscreen emulsions, lotions, creams, sunscreen emulsionsprays, liquid/alcohol sunscreen sprays, sunscreen aqueous gels, broadspectrum sunscreens with UVA and UVB actives, sunscreens with organicand inorganic actives, sunscreens with combinations of organic andinorganic actives, suntan products, self-tanning products, and after sunproducts etc. Particularly suitable compositions are personal careemulsions, more particularly suitable are sun care compositions such assunscreen emulsions and sunscreen emulsion sprays. The personal carecomposition may be in any form, including without limitation in sprays,emulsions, lotions, gels, liquids, sticks, waxes, pastes, powders, andcreams.

The personal care compositions may also include other optionalcomponents commonly used in the industry, and these will vary greatlydepending upon the type of composition and the functionality andproperties desired. Without limitation, these components includethickeners, suspending agents, emulsifiers, UV filters, sunscreenactives, humectants, moisturizers, emollients, oils, waxes, solvents,chelating agents, vitamins, antioxidants, botanical extracts, silicones,neutralizing agents, preservatives, fragrances, dyes, pigments,conditioners, polymers, antiperspirant active ingredients, antiacneagents, anti-dandruff actives, surfactants, exfoliants, film formers,propellants, tanning accelerator, hair fixatives and colors. Thepolymers of the present invention are compatible with most othercomponents used in conventional personal care compositions. For example,sunscreen compositions may contain at least one component selected fromthe group comprising organic UV filters, inorganic UV actives, UVAand/or UVB suncreen actives, octinoxate, octisalate, oxybenzone,homosalate, octocrylene, avobenzene, titanium dioxide, starch,conditioning agents, emulsifiers, other rheology modifiers andthickeners, neutralizers, emollients, solvents, film formers,moisturizers, antioxidants, vitamins, chelating agents, preservatives,fragrances, and zinc oxide. Skin care and cosmetic compositions maycontain at least one component selected from the group consisting ofvitamins, anti-aging agents, moisturizers, emollients, emulsifiers,surfactants, preservatives, pigments, dyes, colors and insectrepellents.

When used in personal care formulations, such as hair care and stylingformulations, for example styling gels, optional additional ingredientscan be added to provide a variety of further additional properties.Various other additives, such as active and functional ingredients, maybe included in the personal care formulation as defined herein. Theseinclude, but are not limited to, emollients, humectants, thickeningagents, electrolytes and salts surfactants, UV light inhibitors,fixative polymers preservatives pigments dyes, colorants, alpha hydroxyacids, aesthetic enhancers such as starch perfumes and fragrances, filmformers (water proofing agents) antiseptics, antifungal, antimicrobialand other medicaments and solvents. Additionally, conditioning agentscan be used in combination with the polymers of this invention, forexample, cationic guar gum, cationic hydroxyethyl cellulose, cationicsynthetic polymers and cationic fatty amine derivatives. These blendedmaterials help to provide more substantivity and effective conditioningproperties in hair. The electrolytes and salts are particularly usefulin boosting the viscosity of the shampoo and improving its suspendingproperties.

Some non-limiting examples of polymers that can used in conjunction withthe polymers of this invention are polyoxythylenated vinylacetate/crotonic acid copolymers, vinyl acetate crotonic acid (90/10)copolymers, vinyl acetate/crotonic acid/vinyl neodecanoate terpolymers,N-octylacrylamide/methylacrylate/hydroxypropyl methacrylate/acrylicacid/tert-butylaminoethyl methacrylate copolymers, and methyl vinylether/maleic anhydride (50/50) copolymers monoesterified with butanol orethanol, acrylic acid/ethyl acrylate/N-tert-butyl-acrylamideterpolymers, and poly (methacrylic acid/acrylamidomethyl propanesulfonic acid), acrylates copolymer,octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,acrylates/octylacrylamide copolymer, VA/crotonates/vinyl Neodeanoatecopolymer, poly(N-vinyl acetamide), poly(N-vinyl formamide), corn starchmodified, sodium polystyrene sulfonate, polyquaterniums such aspolyquaternium-4, polyquaternium-7, polyquaternium-10,polyquaternium-11, polyquartemium-16, polyquaternium-28,polyquaternium-29, polyquaternium-46, polyether-1, polyurethanes,VA/acrylates/lauryl methacrylate copolymer, adipicacid/dimethylaminohydroxypropyl diethylene AMP/acrylates copolymer,methacrylol ethyl betaine/acrylates copolymer,PVP/dimethylaminoethylmethacrylate copolymer, PVP/DMAPA acrylatescopolymer, PVP/vinylcaprolactam/DMAPA acrylates copolymer, vinylcaprolactam/PVP/dimethylaminoethyl methacrylate copolymer, VA/butylmaleate/isobomyl acrylate copolymer, VA/crotonates copolymer,acrylate/acrylamide copolymer, VA/crotonates/vinyl propionate copolymer,vinylpyrrolidone/vinyl acetate/vinyl propionate terpolymers,VA/crotonates, cationic and amphoteric guar, polyvinylpyrrolidone (PVP),polyvinylpyrrolidone/vinyl acetate copolymer, PVP acrylates copolymer,vinyl acetate/crotonic acid/vinyl proprionate, acrylates/acrylamide,acrylates/octylacrylamide, acrylates/hydroxyacrylates copolymer, andalkyl esters of polyvinylmethylether/maleic anhydride,diglycol/cyclohexanedimethanol/isophthalates/sulfoisophthalatescopolymer, vinyl acetate/butyl maleate and isobornyl acrylate copolymer,vinylcaprolactam/PVP/dimethylaminoethyl methacrylate, vinylacetate/alkylmaleate half ester/N-substituted acrylamide terpolymers,vinyl caprolactam/vinylpyrrolidone/methacryloamidopropyltrimethylammonium chloride terpolymer methacrylates/acrylatescopolymer/amine salt, polyvinylcaprolactam, polyurethanes, hydroxypropylguar, hydroxypropyl guar hydroxypropyl trimmonium chloride, poly(methacrylic acid/acrylamidomethyl propane sulfonic acid,poylurethane/acrylate copolymers and hydroxypropyl trimmonium chlorideguar, particularly acrylates copolymer,octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,acrylates/octylacrylamide copolymer, VA/crotonates/vinyl Neodeanoatecopolymer, poly(N-vinyl acetamide), poly(N-vinyl formamide),polyurethane, corn starch modified, sodium polystyrene sulfonate,polyquaternium-4, polyquarternium-10, and polyurethane/acrylatescopolymer.

In addition to the polymers of this invention, the personal carecompositions of the invention may also include a cosmetically acceptableingredient. The ingredient can be a emollient, fragrance. exfoliant,medicament, whitening agent, acne treatment agent, a preservative,vitamins, proteins, a cleanser or conditioning agent.

Examples of cleansers suitable for use the present invention include,but are not limited to, are sodium lauryl sulfate (SLS), sodium laurethsulfate (SLES), ammonium lauryl ether sulfate (ALES), alkanolamides,alkylaryl sulfonates, alkylaryl sulfonic acids, alkylbenzenes, a eacetates, amine oxides, amines, sulfonated amines and amides, betaines,block polymers, carboxylated alcohol or alkylphenol ethoxylates,diphenyl sulfonate derivatives, ethoxylated alcohols, ethoxylatedalkylphenols, ethoxylated amines and/or amides, ethoxylated fatty acids,ethoxylated fatty esters and oils, fatty esters (other than glycol,glycerol, etc.), fluorocarbon-based surfactants, glycerol esters, glycolesters, heterocyclics, imidazolines and imidazoline derivatives,isethionates, lanolin-based derivatives, lecithin and lecithinderivatives, lignin and lignin derivatives, methyl esters,monoglycerides and derivatives, olefin sulfonates, phosphate esters,phosphorous organic derivatives, polymeric (polysaccharides, acrylicacid, acrylamide), propoxylated and ethoxylated fatty acids,propoxylated and ethoxylated fatty alcohols, propoxylated andethoxylated alkyl phenols, protein-based surfactants, quaternarysurfactants, sarcosine derivatives, silicone-based surfactants, soaps,sorbitan derivative, sucrose and glucose esters and derivatives,sulfates and sulfonates of oils and fatty acids, sulfates and sulfonatesethoxylated alkyl phenols, sulfates of alcohols, sulfates of ethoxylatedalcohols, sulfates of fatty esters, sulfonates of benzene, cumene,toluene and xylene, sulfonates of condensed naphthalenes, sulfonates ofdodecyl and tridecyl benzenes, sulfonates of naphthalene and alkylnaphthalene, sulfonates of petroleum, sulfosuccinamates, sulfosuccinatesand derivatives.

Preservatives are often used in personal care formulations to providelong term shelf stability. These can be selected from amongmethylparaben, propylparaben, butylparaben, DMDM hydantoin,imidazolidinyl urea, gluteraldehyde, phenoxyethanol, benzalkoniumchloride, methane ammonium chloride, benzethonium chloride, benzylalcohol, chlorobenzyl alcohol, methylchloroisothiazolinone,methylisothiazolinone, sodium benzoate, chloracetamide, triclosan,iodopropynyl butylcarbamate, sodium pyrithione, and zinc pyrithione.

In an embodiment of this invention, particularly where the hairformulation is a shampoo, the formulation contains a sulfate freesurfactant and the polymers of this invention. Examples of sulfate freesurfactants include, but are not limited to, ethoxylated alkylphenols,ethoxylated amines and/or amides, ethoxylated fatty acids, ethoxylatedfatty esters and oils, fatty esters (other than glycol, glycerol, etc.),fluorocarbon-based surfactants, glycerol esters, glycol esters,heterocyclics, imidazolines and imidazoline derivatives, isethionates,lanolin-based derivatives, lecithin and lecithin derivatives, lignin andlignin derivatives, methyl esters, monoglycerides and derivatives,phosphate esters, phosphorous organic derivatives, polymeric(polysaccharides, acrylic acid, acrylamide), propoxylated andethoxylated fatty acids, propoxylated and ethoxylated fatty alcohols,propoxylated and ethoxylated alkyl phenols, protein-based surfactants,quaternary surfactants, sarcosine derivatives, siliconebasedsurfactants, alpha-olefin sulfonate, alkylaryl sulfonates, sulfonates ofoils and fatty acids, sulfonates of ethoxylated alkyl phenols,sulfonates of benzene, cumene, toluene and xylene, sulfonates ofcondensed naphthalenes, sulfonates of dodecyl and tridecyl benzenes,sulfonates of naphthalene and alkyl naphthalene, sulfonates of petroleumand derivatives thereof. In an embodiment of the invention, the sulfatefree surfactants are sulfonates or ethoxylates.

In another embodiment the formulation contains sulfated surfactants.Some non-limiting examples of sulfated surfactants are sodium laurylsulfate (SLS), sodium laureth sulfate (SLES), alkanolamides, alkylarylsulfonic acids, sulfates of oils and fatty acids, sulfates ofethoxylated alkyl phenols, sulfates of alcohols, sulfates of ethoxylatedalcohols, sulfates of fatty esters, sulfosuccinamates, sulfosuccinatesand derivatives thereof.

In addition to the polymer(s) of this invention, shampoo compositionsmay optionally include other ingredients. Some non-limiting examples ofthese ingredients include, but are not limited to, conditioning agentssuch as silicone oils, either volatile or non-volatile, natural andsynthetic oils. Suitable silicone oils that can be added to thecompositions include dimethicone, dimethiconol, polydimethylsiloxane,silicone oils with various DC fluid ranges from Dow Corning. Suitablenatural oils, such as olive oil, almond oil, avocado oil, wheatgerm oil,ricinus oil and the synthetic oils, such as mineral oil, isopropylmyristate, palmitate, stearate and isostearate, oleyl oleate, isocetylstearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristylmyristate and oleyl erucate can also be used. Some examples of non-ionicconditioning agents are polyols such as glycerin, glycol andderivatives, polyethyleneglycols, which may be known by the trade namesCarbowax® PEG from Union Carbide and Polyox® WSR range from Amerchol,polyglycerin, polyethyleneglycol mono- or di-fatty acid esters.

Suitable cationic polymers that may be used in the formulation are thoseof best known with their CTFA category name Polyquaternium. Someexamples of this class of polymer are Polyquaternium 6, Polyquaternium7, Polyquaternium 10, Polyquaternium 11, Polyquaternium 16,Polyquaternium 22 and Polyquaternium 28, Polyquaternium 4,Polyquaternium 37, Quaternium-8, Quaternium-14, Quaternium-15,Quaternium-18, Quaternium-22, Quaternium-24, Quaternium-26,Quaternium-27, Quaternium-30, Quaternium-33, Quaternium-53,Quaternium-60, Quaternium-61, Quaternium-72, Quaternium-78,Quaternium-80, Quaternium-81, Quaternium-82, Quaternium-83 andQuaternium-84.

Naturally derived cellulose type polymers known as Polymer JR® type fromAmerchol, Polyquaternium 10 or cationic guar gum known with trade nameJaguar® from Rhone-Poulenc, and Guar hydroxypropyl trimonium chloride,chitosan and chitin can also be included in the personal careformulations as cationic natural polymers may also optionally beincluded with the inventive polymers.

The polymers of this invention can also be used in liquid detergentcompositions that include one or more surfactants, such as thoseselected from anionic, nonionic, cationic, amphoteric, and zwitterionicsurfactants. In an embodiment, the preferred surfactants are suitablefor use in isotropic liquid detergent compositions and are mixtures ofanionic and nonionic surfactants although it is to be understood thatany surfactant may be used alone or in combination with any othersurfactant or surfactants. These liquid detergent systems as well as thesurfactants used in them are described in U.S. Pat. No. 6,462,013 whichis incorporated herein by reference in its entirety.

The polymers of this invention may also be used in liquid detergentcompositions and may further optionally comprise at least one additive.Suitable additives may include, for example, builders, dispersants,polymers, ion exchangers, alkalies, anticorrosion materials,antiredeposition materials, antistatic agents, optical brighteners,perfumes, fragrances, dyes, fillers, oils, chelating agents, enzymes,fabric whiteners, brighteners, sudsing control agents, solvents,hydrotropes, bleaching agents, bleach precursors, buffering agents, soilremoval agents, soil release agents, fabric softening agents, andopacifiers. In general, such additives and their amounts are known tothose skilled in the art.

The present invention will now be illustrated by the following examples.The examples are intended to exemplify the present invention but are notintended to limit the scope of the invention in any way. The breadth andscope of the invention are to be limited solely by the claims appendedhereto.

EXAMPLES Measurement of Zero Shear Viscosity

SR-5000 Rheometer (from Rheometrics) was used to measure zero-shearviscosity. Sample was loaded between two 40-mm parallel plates, and thegap of the plate was adjusted to 1.5 mm. Temperature of the sample wascontrol by a peltier. Steady Stress Sweep test was conducted with thefollowing parameters at 25° C. and 45° C.

Sweep Mode=Log

Initial Stress=0.1 Pa

Final Stress=1000.0 Pa

Points Per Decade=10

Max Time Per Data Point=10 s

The flow curve is obtained by plotting viscosity versus shear rate, asshown in FIG. 1. Typically, the flow curve has a “flat” plateau regionof viscosity at low shear rate, followed by a shear-thinning region.Zero-shear viscosity is calculated by taking the average of theviscosity values of the data points in the “flat” plateau region at lowshear rate as shown in FIG. 1.

Example 1

80 grams of a low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel (weight average molecular weight ofapproximately 300,000) was dispersed in 1675 grams of water containing1.6 grams of sodium sulfate in a 2 liter reactor equipped with stirrerand a heating mantle. The mixture was heated to 85° C. while spargingwith nitrogen. 0.356 grams of ferrous ammonium sulfate hexahydratedissolved in 21 grams of water and 8.3 grams of 35% hydrogen peroxidedissolved in 53 grams of water was added. This was then held undernitrogen at 85° C. for 15 minutes to depolymerize the ethyl hydroxyethylcellulose. A monomer feed containing 97.2 grams of methacrylic acid, 120grams of ethyl acrylate, 0.2 grams of diallyl phthalate and 21.43 gramsof C₁₈ alcohol with 20EO itaconate (associative monomer) was then addedover 45 minutes. Concurrently, an initiator solution containing 6.7grams of 35% hydrogen peroxide dissolved in 42.8 grams of water wasadded over 110 minutes. A nitrogen sparge is continued during theseadditions. The reaction mixture was then cooked at 90° C. for an hour.The solution was cooled down to 75° C. and 0.42 g of 70% tert butylhydroperoxide in 2.06 g of water was added in one shot. A solution of0.18 grams of erythorbic acid dissolved in 13.72 grams of water wasadded over 1 hour and then the reaction was held at 70° C. for 30minutes. The reaction product was allowed to cool overnight andseparates out in to an aqueous top phase and a bottom phase that is anopaque white paste which we term the aqueous emulsion paste composition.This aqueous emulsion paste composition had 24.3% polymer with the restbeing water. The polymer portion of this aqueous paste was diluted to 2%and neutralized to pH 7 by slow addition of 50% NaOH. The resultsolution formed a gel which had a viscosity of 95,300 cps at 0.5 rpm asmeasured by a Brookfield viscometer. The polymer composition of theaqueous emulsion paste composition remained a paste for 3 months andlonger and was easily redispersed in water on dilution.

Example 2 Stabilization to Form a Stable Emulsion System

To stabilize the paste as a pourable liquid, the aqueous emulsion pasteof Example 1 can be diluted to 20% polymer with water. Under high shear,guar gum was added as a stabilizer to a total 0.3% of the solution. Thestabilizer was 1.5 weight % of the polysaccharide hydrophobicallymodified alkali swellable rheology modifier in this emulsioncomposition. The resulting product is a stable emulsion composition thatis liquid and pourable.

Example 3 Stabilization to Form a Stable Emulsion System

To stabilize the paste as a pourable liquid, the aqueous emulsion pasteof Example 1 can be diluted to 20% polymer with water. Under high shear,Bermocoll® M 800× (EHEC) from AkzoNobel was added as a stabilizer to atotal 0.3% of the solution. The stabilizer was 1.5 weight % of thepolysaccharide hydrophobically modified alkali swellable rheologymodifier in this emulsion composition. The resulting product is a stableemulsion composition that is liquid and pourable.

Example 4 Stabilization to Form a Stable Emulsion System

To stabilize the paste as a pourable liquid, the aqueous emulsion pasteof Example 1 can be diluted to 20% polymer with water. Under high shear,xanthan gum was added as a stabilizer to a total 5% of the solution. Thestabilizer was 33 weight % of the polysaccharide hydrophobicallymodified alkali swellable rheology modifier in this emulsioncomposition. The resulting product is a stable emulsion composition thatis liquid and pourable.

Example 5 Evaluation of Sample of Example 1 in Personal CareApplications (Shampoo)

200 grams of typical shampoo base was prepared at room temperature byadding 59.58 grams of Deionized water to a 250 ml beaker. A small 1½inch jiffy mixer blade was inserted into the beaker and attached to anoverhead mixer. The batch was allowed to mix with a vortex extending tothe middle of the beaker. Then 24.30 grams (3% active polymer) ofExample lwas added and allowed to mix until uniform. This was followedby adding 62.74 grams of Sodium Laureth Sulfate (25.2% active StandapolES-2 from Cognis Corporation, FairField, N.J.). This was allowed to mixuntil it was homogenous. Then 27.58 grams of Sodium Lauryl sulfate(Witconate WAC LA, Akzo Nobel, Houston, Tex.) was added and mixed untilhomogenous. Then 22.80 grams of Cocamidoproply Betaine (Crodateric CAB30, Croda Inc, Edison, N.J.) was added an allowed to mix untilhomogenous. Then 1.0 grams of DMDM Hydantoin andIodopropynylButylcarbamate Glydant Plus (Liquid), Lonza Corp Allendale,N.J.) was added and the batch was mixed until homogenous. The pH wasthen adjusted to 6.5+/−0.25 using 25% sodium hydroxide (FisherScientific, Fairlawn, N.J.) as needed. Once the batch was uniform 2grams of cosmetic beads, Floraspheres JoJoba MDS beads (Floratech,Chandler, Ariz.) were gently folded into the batch until they wereevenly distributed throughout the batch.

Sample of Example 1 (3.0% Active Solids) pH Viscosity* Rheology 45° C.Suspension Results 6.34 21,300 Quick Flow Passed 8+ weeks to date *RVTDViscometer with Spindle C @ 10 rpm, measure in centipoise (cps.) Thezero shear viscosity of this shampoo was measured to be 1680 Pa-s at 25°C.

To test the suspension properties of the cosmetic beads in this batch itwas placed in a 45° C. oven and the dispersion of the beads was visuallymonitored for migration of the beads. Any sample that showed migrationof the beads was deemed a failure. This batch was tested at the 3.0%active level and had a nice shampoo-like viscosity. The beads stayedsuspended in the sample over an 8 week period at 45° C., as shown in thetop photograph of FIG. 2.

Example 6 Base Shampoo without Example 1 Polymer Composition

200 grams of typical shampoo base was prepared by adding 83.88 grams ofDeionized water to a 250 ml beaker. A small 1½ inch jiffy mixer bladewas inserted into the beaker and attached to an overhead mixer. Thebatch was allowed to mix with a vortex extending to the middle of thebeaker. This was followed by adding 62.74 grams of Sodium LaurethSulfate (25.2% active Standapol ES-2 from Cognis Corporation, FairField,N.J.). This was allowed to mix until it was homogenous. Then 27.58 gramsof Sodium Lauryl sulfate (Witconate WAC LA, Akzo Nobel, Houston, Tex.)was added and mixed until homogenous. Then 22.80 grams of CocamidoproplyBetaine (Crodateric CAB 30, Croda Inc, Edison, N.J.) was added anallowed to mix until homogenous. Then 1.0 grams of DMDM Hydantoin andIodopropynylButylcarbamate Glydant Plus (Liquid), Lonza Corp Allendale,N.J.) was added and the batch was mixed until homogenous. The pH wasthen adjusted to 6.5+/−0.25 using 25% sodium hydroxide (FisherScientific, Fairlawn, N.J.) as needed. Once the batch was uniform 2grams of cosmetic beads, Floraspheres JoJoba MDS beads (Floratech,Chandler, Ariz.) were gently folded into the batch until they wereevenly distributed throughout the batch.

NOTE: The base shampoo without the Sample from Example 1 was also testedfor suspension properties to validate that the base system alone wouldor would not suspend the cosmetic beads. The results are as follows:

Initial pH Viscosity Rheology RT** Suspension Results 6.51 4,000 QuickFlow Failed - beads migrated after a 2 hour period

The base system showed a thin, low viscosity and did not exhibit anysuspension qualities with the beads migrating to the top of the sampleafter a 2 hour period, as shown in the bottom photograph of FIG. 2. Thisproved that the base system needs a suspending agent to have the abilityto suspend the cosmetic beads.

Example 7

80 grams of a maltodextrin C*DRY MD 01955 (DE 5 from Cargill, weightaverage molecular weight in the range 2 to 10,000) was dissolved in 1100grams of water in a 2 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85 C while sparging with nitrogen for1 hour. 0.356 grams of ferrous ammonium sulfate hexahydrate dissolved in21 grams of water and 8.3 grams of 35% hydrogen peroxide dissolved in 53grams of water was added. This was then held under nitrogen at 85° C.for 15 minutes. A monomer feed containing 97.2 grams of methacrylicacid, 120 grams of ethyl acrylate, 0.2 grams of diallyl phthalate and21.43 grams of C₁₈ alcohol with 20EO itaconate (associative monomer) wasthen added over 45 minutes. Concurrently, an initiator solutioncontaining 6.7 grams of 35% hydrogen peroxide dissolved in 42.8 grams ofwater was added over 110 minutes. A nitrogen sparge is continued duringthese additions. The reaction mixture was then cooked at 90° C. for anhour. The final product was a stable emulsion composition with 18.8%solids and the emulsion was stable for 3 months and longer. The residualmethacrylic acid was 12 ppm and the residual level of ethyl acrylate wasundetectable.

Example 8a using Sample from Example 7 in hair gels

The polymer of Example 7 was used in a hair gel and then tested usingthe formula below (Table 3):

TABLE 3 Raw Material % w/w Deionized Water 86.89 Polymer of Example 710.64 Sodium Hydroxide 2.17 (10%) Preservative 0.30 *pH adjusted to 6.50Procedure:

-   -   1. Add Water to container with mixing, using a standard        propeller blade.    -   2. Add Polymer of Example 7 to container with mixing.    -   3. Add Sodium Hydroxide slowly to container to reach desired pH.        Adjust mixing speed as necessary to maintain good turnover.    -   4. Once uniform and clear, add Preservative to container.        Results for Concentration Testing and Clarity

Gels were created using 2-4% active thickening polymer at a pH of 6.5-8(Table 3). Thickening was observed to begin at a pH of 6.3 and continuedto thicken until approximately 7.0. Clarity was observed to increase asthe polymer is neutralized and once finished was under 10 NTU for allsamples, as illustrated in Table 4. This shows equivalent performancewhen compared to a 0.4% Carbomer 980 (rheology modifier from Lubrizol)gel with a value of 5.85 NTU, using the formula in the Table 3.

TABLE 4 Concentration Clarity (active) pH (NTU) 2 6.5 7.37 3 6.5 6.00 46.5 4.81 2 7.0 3.84 3 7.0 2.81 4 7.0 2.80 2 8.0 3.63 3 8.0 3.22 4 8.03.34

Example 8b Polymer of Example 7 in Another Hair Gel Formulation

The following formula was used to create 2 different Hair Gels one withthe polymer of Example 7 and the other with Carbomer 980 (Table 5):

TABLE 5 Raw Material % w/w Deionized Water 76.63 Polymer 7 18.62 PVPK-90 3.0 Aminomethyl Propanol 1.25 Euxyl PE9010 0.50 *pH adjusted to~7.0Procedure:

-   -   1. Add Water to container with mixing using a standard propeller        blade.    -   2. Add Polymer of Example 7 (or Carbomer 980) to container. Mix        well until dispersed fully.    -   3. Add Aminomethyl Propanol to desired pH; continue to mix well.    -   4. Add PVP K-90 (from Ashland) to container. Mix well until        dissolved.    -   5. Add Euxyl PE 9010 (from Schuelke and Mayr). Mix well; gel        will be clear.

These 2 hair gels were evaluated for viscosity using the same methodpreviously used in Example 8a except spindle TC @ 10 rpm was utilized.The results are shown in Table 6.

TABLE 6 Viscosity Sample (cps) pH Polymer of 68100 7.06 Example 7Carbomer 980 69100 6.65Results for Subjective Testing

Hair Gels that were created above were used for subjective evaluations.

The following method was used to perform subjective testing:

10″ long, ¼″ wide, 4.50 g net, European brown hair was wet with waterand gently combed through to remove tangles. 0.50 g of hair gel wasapplied to the swatch and was spread throughout the swatch using atop-to-bottom motion and rotating the swatch for even application.Samples were dried in a 50° C. oven for 1 hour and panelists tested forthe following qualities: Gloss, Stiffness, Dry Comb, Flake, andAnti-Static properties. Dry Feel was omitted from this test for safetypurposes due to possible monomer residuals. A total of 8 sets (16swatches) were evaluated using a standard Ace black comb for combingtests.

It was seen that no statistical differences were seen for any testcategory between the gels made with the Polymer of Example 7 and thegels made with Carbomer 980. Both the gels had similar performance(Table 7).

TABLE 7 Gel made with the Polymer of Example 7 vs. Gel made withCarbomer 980 (from Lubrizol) Dry Gloss Stiffness Comb Flake AntiStat = == = =

Example 9

63 grams of a maltodextrin C*DRY MD 01955 (DE 5 from Cargill) wasdissolved in 467 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for 1 hour. 0.192 grams of ferrous ammoniumsulfate hexahydrate dissolved in 21 grams of water and 8.3 grams of 35%hydrogen peroxide dissolved in 53 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 minutes. A monomer feedcontaining 92.2 grams of methacrylic acid, 67.7 grams of ethyl acrylate,20.7 grams of methyl methacrylate and 7.5 grams of C₁₆ alcohol with 20EO itaconate (associative monomer) was then added over 45 minutes.Concurrently, an initiator solution containing 6.7 grams of 35% hydrogenperoxide dissolved in 42.8 grams of water was added over 110 minutes.The clear solution started to look like an opaque white emulsion 10minutes in to the feed. A nitrogen sparge is continued during theseadditions. The reaction mixture was then cooked at 90° C. for an hour.The final product was a stable emulsion composition with 28.1% solidsand the emulsion was stable for 3 months and longer. The starch was 25weight percent of the total polymer.

Example 10

91 grams of a maltodextrin C*DRY MD 01955 (DE 5 from Cargill) wasdissolved in 663 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for 1 hour. A monomer solution containing 120grams of methacrylic acid, 89.47 grams of ethyl acrylate, 27.1 grams ofmethyl methacrylate and 9.4 grams of C₁₆ alcohol with 20EO itaconate(associative monomer) was prepared. 5 weight percent of this monomermixture was added to the reactor. At the same time 0.27 grams ofammonium persulfate dissolved in 28.4 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N2. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.12 grams of ammonium persulfate dissolved in 45grams of water was added over 120 minutes. The clear solution started tolook like an opaque white emulsion 30 minutes in to the feed. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 85 C for an hour. A solution of 0.18 grams of ammoniumpersulfate dissolved in 48 grams of water was added over 1 hour and thenthe reaction was held at 85° C. for 30 minutes. The final product was astable emulsion composition with 30% solids and the emulsion was stablefor 3 months and longer.

Example 11

91 grams of a maltodextrin C*DRY MD 01955 (DE 5 from Cargill) wasdissolved in 663 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for 1 hour. A monomer solution containing 120grams of methacrylic acid, 89.47 grams of ethyl acrylate, 27.1 grams ofmethyl methacrylate, 0.23 grams of diallyl phthalate and 9.4 grams ofC₁₆ alcohol with 20EO itaconate (associative monomer) was prepared. 5weight percent of this monomer mixture was added to the reactor. At thesame time 0.27 grams of ammonium persulfate dissolved in 28.4 grams ofwater was added. The reaction mixture was held at 85° C. for 15 minutesunder N2. The rest of the monomer was then added over 90 minutes.Concurrently, an initiator solution containing 0.12 grams of ammoniumpersulfate dissolved in 45 grams of water was added over 120 minutes.The clear solution started to look like an opaque white emulsion 30minutes in to the feed. A nitrogen sparge is continued during theseadditions. The reaction mixture was then cooked at 85 C for an hour. Asolution of 0.18 grams of ammonium persulfate dissolved in 48 grams ofwater was added over 1 hour and then the reaction was held at 85° C. for30 minutes. The final product was a stable emulsion composition with 30%solids and the emulsion was stable for 3 months and longer.

Example 12

The polymers of the Examples 7, 9, 10 and 11 were diluted to the levelsshown in Table 8. They were then neutralized to pH 8 using 10% NaOH. Theviscosity of these solutions at different rpms was measured using aBrookfield viscometer. These data indicate that these polymers are goodalkali swellable rheology modifiers.

TABLE 8 Polymer of % Polymer Viscosity (cps) @ different rpms ExampleSolids dosage 0.5 5 10 20 50 7 18.8 1 4000 1280 880 620 380 2 12000021600 13700 8350 4920 9 28.1 5 32000 14000 10700 8000 5060 10 29.6 12000 680 520 410 324 2 3600 2800 2380 1960 1432 4 28000 19400 1520011050 6940 11 29.7 1 800 360 280 230 200 2 31600 7480 4980 3380 2136 4158000 31200 18800 12250 7080

Example 13

91 grams of a 85% Perfectamyl A4692 (oxidized potato starch from Avebewith a weight average molecular weight of 510,000) was dissolved in 706grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 101.7 grams of methacrylicacid, 125.9 grams of ethyl acrylate, 0.24 grams of diallyl phthalate and22.4 grams of C₁₈ alcohol with 20EO itaconate (associative monomer) wasprepared. 5 weight percent of this monomer mixture was added to thereactor. At the same time 0.27 grams of ammonium persulfate dissolved in19.8 grams of water was added. The reaction mixture was held at 85° C.for 15 minutes under N2. The rest of the monomer was then added over 90minutes. Concurrently, an initiator solution containing 0.17 grams ofammonium persulfate dissolved in 45 grams of water was added over 120minutes. A nitrogen sparge was continued during these additions. Thereaction mixture was then cooked at 85° C. for an hour. A solution of0.17 grams of ammonium persulfate dissolved in 48 grams of water wasadded over 1 hour and then the reaction was held at 85° C. for 30minutes. The final product was an emulsion composition with 29% solidsand pH 4.3 with an average particle size in the range 1600-1900 nm. Theemulsion changed in to an aqueous emulsion paste composition with aweek. The residual ethylacrylate content was 242 ppm of the solution.

The aqueous emulsion paste composition was diluted to 2% solids and thenneutralized to pH 7.5 using 10% NaOH. This formed a gel that suspendedbeads for at least one week at 45° C.

Example 14

91 grams of C*DRY MD 01955 (DE 5 from Cargill) was dissolved in 706grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 101.7 grams of methacrylicacid, 125.9 grams of ethyl acrylate, 0.29 grams of trimethylolpropanetriacrylate and 22.4 grams of C₁₈ alcohol with 20EO itaconate(associative monomer) was prepared. 5 weight percent of this monomermixture was added to the reactor. At the same time 0.27 grams ofammonium persulfate dissolved in 19.8 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N2. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.17 grams of ammonium persulfate dissolved in 45grams of water was added over 120 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour. A solution of 0.17 grams of ammonium persulfatedissolved in 48 grams of water was added over 1 hour and then thereaction was held at 85° C. for 30 minutes. The final product was astable emulsion composition with 28% solids with an average particlesize in the range 300 nm and was stable for at least a month at 25° C.

Example 15

177 grams of C*DRY MD 01955 (DE 5 from Cargill) was dissolved in 706grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 69.3 grams of methacrylicacid, 85.7 grams of ethyl acrylate, 0.16 grams of diallyl phthalate and15.3 grams of C₁₈ alcohol with 20EO itaconate (associative monomer) wasprepared. 5 weight percent of this monomer mixture was added to thereactor. At the same time 0.18 grams of ammonium persulfate dissolved in19.8 grams of water was added. The reaction mixture was held at 85° C.for 15 minutes under N2. The rest of the monomer was then added over 90minutes. Concurrently, an initiator solution containing 0.12 grams ofammonium persulfate dissolved in 45 grams of water was added over 120minutes. A nitrogen sparge was continued during these additions. Thereaction mixture was then cooked at 85° C. for an hour. A solution of0.11 grams of ammonium persulfate dissolved in 48 grams of water wasadded over 1 hour and then the reaction was held at 85° C. for 30minutes. The final product was a stable emulsion composition with 29%solids with an average particle size in the range 200 nm. Thepolysaccharide was approximately 50 weight percent of the combinedweight of the polysaccharide and the monomers.

Example 16

89.5 grams of a 94% Stackote 8 (depolymerized dent starch from Ingredionwith a weight average molecular weight of 600,000) was dissolved in 646grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 93.1 grams of methacrylicacid, 115.2 grams of ethyl acrylate, 0.22 grams of diallyl phthalate and20.5 grams of C₁₈ alcohol with 20 EO itaconate (associative monomer) wasprepared. 5 weight percent of this monomer mixture was added to thereactor. At the same time 0.25 grams of ammonium persulfate dissolved in18.1 grams of water was added. The reaction mixture was held at 85° C.for 15 minutes under N2. The rest of the monomer was then added over 90minutes. Concurrently, an initiator solution containing 0.17 grams ofammonium persulfate dissolved in 42 grams of water was added over 120minutes. A nitrogen sparge was continued during these additions. Thereaction mixture was then cooked at 85° C. for an hour. A solution of0.15 grams of ammonium persulfate dissolved in 7 grams of water wasadded over 0.5 hours and then the reaction was held at 85° C. for 30minutes. The final product was an emulsion composition with 22% solidswith an average particle size of around 160 nm.

Example 17

111.4 grams of a 83% Perfectamyl LV (oxidized potato starch from Avebewith a weight average molecular weight of 240,000) was dissolved in 706grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85 C while sparging with nitrogen forone hour. A monomer solution containing 101.7 grams of methacrylic acid,125.9 grams of ethyl acrylate, 0.24 grams of diallyl phthalate and 22.4grams of C₁₈ alcohol with 20 EO itaconate (associative monomer) wasprepared. 5 weight percent of this monomer mixture was added to thereactor. At the same time 0.27 grams of ammonium persulfate dissolved in19.8 grams of water was added. The reaction mixture was held at 85° C.for 15 minutes under N2. The rest of the monomer was then added over 90minutes. Concurrently, an initiator solution containing 0.17 grams ofammonium persulfate dissolved in 45 grams of water was added over 120minutes. A nitrogen sparge was continued during these additions. Thereaction mixture was then cooked at 85° C. for an hour. A solution of0.16 grams of ammonium persulfate dissolved in 7 grams of water wasadded over 15 minutes and then the reaction was held at 85° C. for 30minutes. The final product was an emulsion composition with 29% solidswith an average particle size in the range 860 nm. The emulsioncomposition changed to a stable aqueous emulsion paste compositionwithin a week.

Example 18

91 grams of C*DRY MD 01955 (DE 5 from Cargill) was dissolved in 706grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 101.7 grams of methacrylicacid, 125.9 grams of ethyl acrylate, 0.24 grams of diallyl phthalate and22.4 grams of C₁₈ alcohol with 20EO itaconate (associative monomer) wasprepared. 5 weight percent of this monomer mixture was added to thereactor. At the same time 0.18 grams of ammonium persulfate dissolved in19.8 grams of water was added. The reaction mixture was held at 85° C.for 15 minutes under N2. The rest of the monomer was then added over 90minutes. Concurrently, an initiator solution containing 0.17 grams ofammonium persulfate dissolved in 45 grams of water was added over 120minutes. A nitrogen sparge was continued during these additions. Thereaction mixture was then cooked at 85° C. for an hour. A solution of0.16 grams of ammonium persulfate dissolved in 7 grams of water wasadded over 10 minutes and then the reaction was held at 85° C. for 30minutes. The final product was a stable emulsion composition with 29%solids and a pH of 3.2 with an average particle size in the range 500nm. The residual ethyl acrylate level was 121 ppm.

Example 19

103 grams of Thermflo (lightly crosslinked waxy maize starch fromIngredion) was dissolved in 956 grams of water in a 1 liter reactorequipped with stirrer and a heating mantle. The mixture was heated to95° C. while sparging with nitrogen for one hour. 10 grams of 35%hydrogen peroxide was added and held at 95° C. for 3 hours. The reactionwas then cooled to 85° C. A monomer solution containing 101.7 grams ofmethacrylic acid, 125.9 grams of ethyl acrylate, 0.24 grams of diallylphthalate and 22.4 grams of C₁₈ alcohol with 20 EO itaconate(associative monomer) was prepared. 5 weight percent of this monomermixture was added to the reactor. At the same time 0.27 grams ofammonium persulfate dissolved in 19.8 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N2. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.17 grams of ammonium persulfate dissolved in 45grams of water was added over 120 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour. A solution of 0.16 grams of ammonium persulfatedissolved in 7 grams of water was added over 10 minutes and then thereaction was held at 85° C. for 30 minutes. The final product was astable emulsion composition with 21.7% solids and a pH of 2.8 with anaverage particle size in the range 400 nm.

Example 20

56.0 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dissolved in 837.5 grams of watercontaining 1.12 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1781 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.15 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 mins to depolymerize the ethylhydroxyethyl cellulose. A monomer feed containing 42.27 grams ofmethacrylic acid, 52.32 grams of ethyl acrylate, 0.10 grams of diallylphthalate and 9.32 grams of C₁₈ alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. The EHEC was 35weight percent of the total weight of the EHEC and monomer.Concurrently, an initiator solution containing 3.35 grams of 35%hydrogen peroxide dissolved in 21.42 grams of water was added. Anitrogen sparge is continued during these additions. The reactionmixture was then cooked at 90° C. for an hour. The reaction product wasallowed to cool overnight and separates out in to an aqueous top phaseand a bottom phase that is an opaque white paste which was the aqueousemulsion paste composition. This aqueous emulsion paste compositionweighed approximately 700 grams and had 18.05% polymer with the restbeing water. The polymer portion of this aqueous emulsion pastecomposition was diluted to 2% and neutralized to pH 8 by slow additionof 10% NaOH. The result solution formed a gel which had a viscosity of33,600 cps at 0.5 rpm. The polymer of the aqueous emulsion pastecomposition remained a paste for 3 months and longer and was easilyredispersed in water on dilution.

Example 21

42.11 grams of an 85% Perfectamyl A4692 (oxidized potato starch fromAvebe with a weight average molecular weight of 510,000) was dissolvedin 837.5 grams of water in a 1 liter reactor equipped with stirrer and aheating mantle. The mixture was heated to 85° C. while sparging withnitrogen. 0.1781 grams of ferrous ammonium sulfate hexahydrate dissolvedin 10.57 grams of water and 4.15 grams of 35% hydrogen peroxidedissolved in 26.51 grams of water was added. This was then held undernitrogen at 85° C. for 15 mins to depolymerize the potato starch. Amonomer feed containing 48.62 grams of methacrylic acid, 60.17 grams ofethyl acrylate, 0.12 grams of diallyl phthalate and 10.72 grams of C₁₈methylamine with 20 EO itaconate (associative monomer) was then addedover 45 minutes. Concurrently, an initiator solution containing 3.35grams of 35% hydrogen peroxide dissolved in 21.42 grams of water wasadded. A nitrogen sparge is continued during these additions. Thereaction mixture was then cooked at 90° C. for an hour. The solution wascooled down to 75° C. and 0.42 g of 70% tert butyl hydroperoxide in 2.06g of water was added in one shot. A solution of 0.18 grams of erythorbicacid dissolved in 13.72 grams of water was added over 1 hour and thenthe reaction was held at 70° C. for 30 minutes. The final product was astable emulsion composition with 14.0% solids. The solution was dilutedto 3% and neutralized to pH 8 by slow addition of 10% NaOH. The resultsolution formed a gel which had a viscosity of 350,000 cps at 0.5 rpm.

Example 22

42.11 grams of an 85% Perfectamyl A4692 (oxidized potato starch fromAvebe with a weight average molecular weight of 510,000) was dissolvedin 832.14 grams of water in a 1 liter reactor equipped with stirrer anda heating mantle. The mixture was heated to 85° C. while sparging withnitrogen. 0.1781 grams of ferrous ammonium sulfate hexahydrate dissolvedin 10.57 grams of water and 4.15 grams of 35% hydrogen peroxidedissolved in 26.51 grams of water was added. This was then held undernitrogen at 85° C. for 15 mins to depolymerize the potato starch. Amonomer feed containing 43.26 grams of methacrylic acid, 60.17 grams ofethyl acrylate, 0.12 grams of diallyl phthalate and 21.43 grams of aurethane associate monomer (3-isopropenyl-α,α-dimethylbenzyl isocyanatereacted with alcohol ethoxylate (C18 with 25 moles of ethoxylate) toform the corresponding urethane monomer) was then added over 45 minutes.Concurrently, an initiator solution containing 3.35 grams of 35%hydrogen peroxide dissolved in 21.42 grams of water was added. Anitrogen sparge is continued during these additions. The reactionmixture was then cooked at 90° C. for an hour. The solution was cooleddown to 75° C. and 0.42 g of 70% tert butyl hydroperoxide in 2.06 g ofwater was added. A solution of 0.18 grams of erythorbic acid dissolvedin 13.72 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product was a stable emulsionwith 13.1% solids. The solution was diluted to 3% and neutralized to pH8 by slow addition of 10% NaOH. The result solution formed a gel whichhad a viscosity of 218,000 cps at 0.5 rpm.

Example 23

58.95 grams of an 85% Perfectamyl A4692 (oxidized potato starch fromAvebe with a weight average molecular weight of 510,000) was dissolvedin 575.44 grams of water in a 1 liter reactor equipped with stirrer anda heating mantle. The mixture was heated to 85° C. while sparging withnitrogen. 0.2494 grams of ferrous ammonium sulfate hexahydrate dissolvedin 7.00 grams of water and 5.81 grams of 35% hydrogen peroxide dissolvedin 14.00 grams of water was added. This was then held under nitrogen at85° C. for 15 mins to depolymerize the potato starch. A monomer feedcontaining 60.56 grams of methacrylic acid, 84.24 grams of ethylacrylate, 0.16 grams of diallyl phthalate and 30.00 grams of CD 559associative monomer mixture (50% C₁₆₋₁₈ alcohol with 20EO, 25%methacrylic acid and 25% water) was then added over 45 minutes.Concurrently, an initiator solution containing 4.69 grams of 35%hydrogen peroxide dissolved in 29.98 grams of water was added. Anitrogen sparge is continued during these additions. The reactionmixture was then cooked at 90° C. for an hour. The solution was cooleddown to 75° C. and 0.58 of 70% tert butyl hydroperoxide in 2.88 g ofwater was added. A solution of 0.25 grams of erythorbic acid dissolvedin 19.21 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product was a stable emulsioncomposition with 24.3% solids. The solution was diluted to 3% andneutralized to pH 8 by slow addition of 10% NaOH. The result solutionformed a gel which had a viscosity of 158,000 cps at 0.5 rpm.

Example 24

66.53 grams of an 85% Perfectamyl A4692 (oxidized potato starch fromAvebe with a weight average molecular weight of 510,000) was dissolvedin 649.38 grams of water in a 1 liter reactor equipped with stirrer anda heating mantle. The mixture was heated to 85° C. while sparging withnitrogen. 0.2814 grams of ferrous ammonium sulfate hexahydrate dissolvedin 7.90 grams of water and 6.55 grams of 35% hydrogen peroxide dissolvedin 15.80 grams of water was added. This was then held under nitrogen at85° C. for 5 mins to depolymerize the potato starch. A monomer feedcontaining 76.81 grams of methacrylic acid, 95.07 grams of ethylacrylate, 0.18 grams of diallyl phthalate and 33.86 grams of CD 559associative monomer mixture (50% C₁₆₋₁₈ alcohol with 20 EO, 25%methacrylic acid and 25% water) was then added over 45 minutes.Concurrently, an initiator solution containing 5.29 grams of 35%hydrogen peroxide dissolved in 33.84 grams of water was added. Anitrogen sparge is continued during these additions. The reactionmixture was then cooked at 90° C. for an hour. The solution was cooleddown to 75° C. and 0.66 of 70% tert butyl hydroperoxide in 3.25 g ofwater was added. A solution of 0.29 grams of erythorbic acid dissolvedin 21.68 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product was a stable emulsioncomposition with 19.4% solids. The solution was diluted to 3% andneutralized to pH 8 by slow addition of 10% NaOH. The result solutionformed a gel which had a viscosity of 318,000 cps at 0.5 rpm.

Example 25

66.53 grams of an 85% Perfectamyl A4692 (oxidized potato starch fromAvebe with a weight average molecular weight of 510,000) was dissolvedin 649.38 grams of water in a 1 liter reactor equipped with stirrer anda heating mantle. The mixture was heated to 85° C. while sparging withnitrogen. 0.2814 grams of ferrous ammonium sulfate hexahydrate dissolvedin 7.90 grams of water and 6.55 grams of 35% hydrogen peroxide dissolvedin 15.80 grams of water was added. This was then held under nitrogen at85° C. for 10 mins to depolymerize the potato starch. A monomer feedcontaining 76.81 grams of methacrylic acid, 95.07 grams of ethylacrylate, 0.18 grams of diallyl phthalate and 33.86 grams of CD 559associative monomer mixture (50% C₁₆₋₁₈ alcohol with 20 EO, 25%methacrylic acid and 25% water) was then added over 45 minutes.Concurrently, an initiator solution containing 5.29 grams of 35%hydrogen peroxide dissolved in 33.84 grams of water was added. Anitrogen sparge is continued during these additions. The reactionmixture was then cooked at 90° C. for an hour. The solution was cooleddown to 75° C. and 0.66 of 70% tert butyl hydroperoxide in 3.25 g ofwater was added. A solution of 0.29 grams of erythorbic acid dissolvedin 21.68 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product was a stable emulsioncomposition with 24.1% solids. The solution was diluted to 3% andneutralized to pH 8 by slow addition of 10% NaOH. The result solutionformed a gel which had a viscosity of 280,000 cps at 0.5 rpm.

Example 26

66.53 grams of an 85% Perfectamyl A4692 (oxidized potato starch fromAvebe with a weight average molecular weight of 510,000) was dissolvedin 649.38 grams of water in a 1 liter reactor equipped with stirrer anda heating mantle. The mixture was heated to 85° C. while sparging withnitrogen. 0.2814 grams of ferrous ammonium sulfate hexahydrate dissolvedin 7.90 grams of water and 6.55 grams of 35% hydrogen peroxide dissolvedin 15.80 grams of water was added. Immediately, a monomer feedcontaining 76.81 grams of methacrylic acid, 95.07 grams of ethylacrylate, 0.18 grams of diallyl phthalate and 33.86 grams of CD 559associative monomer mixture (50% C₁₆₋₁₈ alcohol with 20EO, 25%methacrylic acid and 25% water) was then added over 45 minutes.Concurrently, an initiator solution containing 5.29 grams of 35%hydrogen peroxide dissolved in 33.84 grams of water was added. Anitrogen sparge is continued during these additions. The reactionmixture was then cooked at 90° C. for an hour. The solution was cooleddown to 75° C. and 0.66 of 70% tert butyl hydroperoxide in 3.25 g ofwater was added. A solution of 0.29 grams of erythorbic acid dissolvedin 21.68 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product was a stable emulsionwith 23.8% solids. The solution was diluted to 3% and neutralized to pH8 by slow addition of 10% NaOH. The result solution formed a gel whichhad a viscosity of 284,000 cps at 0.5 rpm.

Example 27

26.97 grams of a Kleptose, a beta cyclodextrin from Roquette, wasdissolved in 837.5 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen. A monomer feed containing 55.14 grams ofmethacrylic acid, 68.25 grams of ethyl acrylate, 0.13 grams of diallylphthalate and 12.15 grams of C₁₈ alcohol with 20EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 0.22 grams of ammonium persulfatedissolved in 21.42 grams of water was added. A nitrogen sparge iscontinued during these additions. The reaction mixture was then cookedat 90° C. for an hour. The solution was cooled down to 75° C. and 0.42 gof 70% tert butyl hydroperoxide in 2.06 g of water was added. A solutionof 0.18 grams of erythorbic acid dissolved in 13.72 grams of water wasadded over 1 hour and then the reaction was held at 70° C. for 30minutes. The final product was a stable emulsion with 13.7% solids. Thesolution was diluted to 3% and neutralized to pH 8 by slow addition of10% NaOH.

Example 28

48 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 837.5 grams of watercontaining 0.96 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1781 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.15 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 45.52 grams ofmethacrylic acid, 56.34 grams of ethyl acrylate, 0.11 grams of diallylphthalate and 10.03 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.35 grams of 35% hydrogen peroxidedissolved in 21.42 grams of water was added over 60 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The reaction product was allowed tocool overnight and separates out in to an aqueous top phase and a bottomphase that is an opaque white paste which we term the aqueous emulsionpaste. This aqueous emulsion paste phase had 21.8% polymer with the restbeing water. The polymer portion of this aqueous paste was diluted to 2%and neutralized to pH 7 by slow addition of 10% NaOH. The resultsolution formed a gel which had a viscosity of 20,000 cps at 0.5 rpm asmeasured by a Brookfield viscometer. The polymer of the aqueous emulsionpaste remained a paste for 3 months and longer and was easilyredispersed in water on dilution.

Example 29

104.0 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 837.5 grams of watercontaining 1.12 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1781 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.15 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 22.76 grams ofmethacrylic acid, 28.17 grams of ethyl acrylate, 0.05 grams of diallylphthalate and 5.02 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 30 minutes. The polysaccharidecontent was approximately 65 weight percent of the polysaccharide andmonomer. Concurrently, an initiator solution containing 3.35 grams of35% hydrogen peroxide dissolved in 21.42 grams of water was added over50 minutes. A nitrogen sparge is continued during these additions. Thereaction mixture was then cooked at 90° C. for an hour. The finalproduct was a single phase, very viscous liquid with 13.14% solids. Thesolution was diluted to 2% and neutralized to pH 8 by slow addition of10% NaOH. The result solution formed a gel which had a viscosity of7,840 cps at 0.5 rpm as measured by a Brookfield viscometer. The polymerof the aqueous emulsion paste remained a paste for 3 months and longerand was easily redispersed in water on dilution.

Example 30

59 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 676.81 grams of watercontaining 2.71 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. A monomer mixture containing 59.69 gramsof dimethyl aminoethyl methacrylate, 96.11 grams of ethyl acrylate and8.22 grams of C16 alcohol with 20 EO itaconate (associative monomer) wasprepared and mixed for an hour. 5% of the monomer mix was added to thereactor when the temperature reached 85° C. At this point, a solution of0.16 grams of ammonium persulfate in 37.90 grams water was added to thereactor. Reactor was then held under nitrogen at 85° C. for 15 mins. Atthe end of the 15 minutes, rest of the monomer mix was feed over 45minutes. Concurrently, an initiator solution containing 0.08 grams ofammonium persulfate dissolved in 41.96 grams of water was added over 70minutes. A nitrogen sparge is continued during these additions. Thereaction mixture was then cooked at 85° C. for an hour. The solution wascooled down to 75° C. and 0.07 grams of ammonium persulfate in 24.37grams of water was added. The final product was a viscous, creamy whiteemulsion with 20% solids. The solution was diluted to 5% and neutralizedto pH 3 by slow addition of citric acid. There was no rheology buildup.

Example 31

40 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 837.5 grams of watercontaining 0.8 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1781 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.15 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 48.61 grams ofmethacrylic acid, 60.17 grams of ethyl acrylate, 0.11 grams of diallylphthalate and 10.72 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.35 grams of 35% hydrogen peroxidedissolved in 21.42 grams of water was added over 60 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The solution was cooled down to 75°C. The final product separated out in to an aqueous top phase and abottom phase that is an opaque white paste which we term the aqueousemulsion paste. This aqueous emulsion paste phase had 25.04% polymerwith the rest being water. The polymer portion of this aqueous paste wasdiluted to 2% and neutralized to pH 8 by slow addition of 10% NaOH. Theresult solution formed a gel which had a viscosity of 33,600 cps at 0.5rpm as measured by a Brookfield viscometer. The polymer of the aqueousemulsion paste remained a paste for 3 months and longer and was easilyredispersed in water on dilution.

Example 32

40 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 822.5 grams of watercontaining 4.0 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1781 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.15 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. When thetemperature reached 85° C., a monomer feed containing 48.61 grams ofmethacrylic acid, 60.17 grams of ethyl acrylate, 0.11 grams of diallylphthalate and 10.72 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.35 grams of 35% hydrogen peroxidedissolved in 21.42 grams of water was added over 60 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The solution was cooled down to 75°C. and 0.31 grams of 70% tert butyl hydroperoxide in 10.00 grams ofwater was added. A solution of 0.14 grams of erythorbic acid dissolvedin 10.00 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product separated out in to anaqueous top phase and a bottom phase that is an opaque white paste whichwe term the aqueous emulsion paste. This aqueous emulsion paste phasehad 18.1% polymer with the rest being water.

Example 33

40 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 837.5 grams of watercontaining 0.8 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1781 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.15 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 30 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 48.61 grams ofmethacrylic acid, 60.17 grams of ethyl acrylate, 0.11 grams of diallylphthalate and 10.72 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.35 grams of 35% hydrogen peroxidedissolved in 21.42 grams of water was added over 60 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The final product separated out in toan aqueous top phase and a bottom phase that is an opaque white pastewhich we term the aqueous emulsion paste. This aqueous emulsion pastephase had 26.5% polymer with the rest being water.

Example 34

40 grams of a low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 837.5 grams of watercontaining 20 grams of sodium sulfate in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen. 0.1781 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.16 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 48.77 grams ofmethacrylic acid, 60.36 grams of ethyl acrylate, 0.12 grams of diallylphthalate and 10.75 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.36 grams of 35% hydrogen peroxidedissolved in 21.42 grams of water was added over 110 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The final product separated out in toan aqueous top phase and a bottom phase that is an opaque white pastewhich we term the aqueous emulsion paste. This aqueous emulsion pastephase had 24.3% polymer with the rest being water.

Example 35

25.26 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 837.5 grams of watercontaining 0.48 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1069 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 4.72 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 55.27 grams ofmethacrylic acid, 68.41 grams of ethyl acrylate, 0.13 grams of diallylphthalate and 12.18 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.81 grams of 35% hydrogen peroxidedissolved in 21.42 grams of water was added over 110 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The final product separated out in toan aqueous top phase and a bottom phase that is an opaque white pastewhich we term the aqueous emulsion paste. This aqueous emulsion pastephase had 22.3% polymer with the rest being water.

Example 36

15.16 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 837.5 grams of watercontaining 0.29 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.0641 grams of ferrous ammonium sulfatehexahydrate dissolved in 10.57 grams of water and 5.05 grams of 35%hydrogen peroxide dissolved in 26.51 grams of water was added. This wasthen held under nitrogen at 85° C. for 15 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 59.18 grams ofmethacrylic acid, 73.24 grams of ethyl acrylate, 0.14 grams of diallylphthalate and 13.04 grams of C18 alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.81 grams of 35% hydrogen peroxidedissolved in 21.42 grams of water was added over 110 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The final product separated out in toan aqueous top phase and a bottom phase that is an opaque white pastewhich we term the aqueous emulsion paste. This aqueous emulsion pastephase had 26.3% polymer with the rest being water.

Example 37

38.74 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 770.5 grams of watercontaining 0.74 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1639 grams of ferrous ammonium sulfatehexahydrate dissolved in 9.72 grams of water and 3.82 grams of 35%hydrogen peroxide dissolved in 24.39 grams of water was added. This wasthen held under nitrogen at 85° C. for 5 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 44.73 grams ofmethacrylic acid, 55.36 grams of ethyl acrylate, 0.11 grams of diallylphthalate and 9.86 grams of C₁₈ alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.08 grams of 35% hydrogen peroxidedissolved in 19.70 grams of water was added over 60 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The solution was cooled down to 75°C. and 0.38 grams of 70% tert butyl hydroperoxide in 1.90 grams of waterwas added. A solution of 0.17 grams of erythorbic acid dissolved in12.62 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product separated out in to anaqueous top phase and a bottom phase that is an opaque white paste whichwe term the aqueous emulsion paste. This aqueous emulsion paste phasehad 27.5% polymer with the rest being water

Example 38

38.74 grams of low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel was dispersed in 770.5 grams of watercontaining 0.74 grams of sodium sulfate in a 1 liter reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen. 0.1639 grams of ferrous ammonium sulfatehexahydrate dissolved in 9.72 grams of water and 3.82 grams of 35%hydrogen peroxide dissolved in 24.39 grams of water was added. This wasthen held under nitrogen at 85° C. for 60 minutes to depolymerize theethyl hydroxyethyl cellulose. A monomer feed containing 44.73 grams ofmethacrylic acid, 55.36 grams of ethyl acrylate, 0.11 grams of diallylphthalate and 9.86 grams of C₁₈ alcohol with 20 EO itaconate(associative monomer) was then added over 45 minutes. Concurrently, aninitiator solution containing 3.08 grams of 35% hydrogen peroxidedissolved in 19.70 grams of water was added over 60 minutes. A nitrogensparge is continued during these additions. The reaction mixture wasthen cooked at 90° C. for an hour. The solution was cooled down to 75°C. and 0.38 grams of 70% tert butyl hydroperoxide in 1.90 grams of waterwas added. A solution of 0.17 grams of erythorbic acid dissolved in12.62 grams of water was added over 1 hour and then the reaction washeld at 70° C. for 30 minutes. The final product separated out in to anaqueous top phase and a bottom phase that is an opaque white paste whichwe term the aqueous emulsion paste. This aqueous emulsion paste phasehad 28.7% polymer with the rest being water.

Example 39

The polymers of this invention were compared to the performance of acommercial polymer (Alcogum L-344 from AkzoNobel Surface Chemistry) inthe paint formulation shown below in Table 9.

TABLE 9 Weight Materials percent Water 27.85 Cellulose ether (Prime35000.3 from AkzoNobel) 2-amino-2-methyl-1- 0.15 propanol (AMP95) DefoamerDispelair CF-246 0.2 from Blackburn Chemicals Ltd. Dispersant sodium 0.5polyacrylate Wetting agent (EF-406 from 0.2 Dow) Titanium dioxide (Tiona595 18 from Cristal Global) Calcium carbonate (CC- 15 1000) Kaolin(Jufeng from Shanxi 6 Jufeng Kaolin Co) Defoamer (Dispelair CF-246) 0.2Bactericide 1 2- 0.2 benzisothiazol-3(2h)-one Coalescing agent (Texanol2 from Eastman) Propylene glycol (PG) 1 Acrylic Emulsion (Primal 25AC-261 from Dow) Polymer (active) 0.12 Water rest

The paint was made based on the above exterior wall paint formulation.The pH of the final formulation was adjusted to range 8.5˜8.8 as shownbelow in Table 10.

TABLE 10 Alcogum L-344 Example 7 Example 13 pH 8.58 8.62 8.77

1. ICI Viscosity

The ICI viscosity measured by an ICI viscometer in Pascals is evaluatedunder high shear rate. This corresponds to the processes of rollercoating and spraying during the end use application.

TABLE 11 Polymer ICI viscosity (Pa) Alcogum L-344 0.58 Example 7  0.58Example 13 0.59

As shown in Table 11, the ICI viscosity of paints with Alcogum and thetwo polymers of this invention are nearly identical.

2. Brookfield Viscosity

Brookfield viscosity (measured in centipoise/cP) is evaluated under lowshear rate and is a measure of levelling, sagging and settling in paintand coating applications. The meter is Brookfield viscometer using cP asa unit. Table 12 shows the Brookfield viscosity of paints underdifferent rotate speed conditions (0.3 rpm, 6 rpm and 60 rpm).

TABLE 12 Brookfield Viscosity (cP) Ratio Polymer 0.3 rpm 6 rpm 60 rpm(0.3/60 rpm) L-344 112000 12100 2480 45.16 Example 7  115000 12933 270742.48 Example 13 130000 13600 2760 47.10

The Ratio listed in the last column of Table 12 is the ratio of the 0.3rpm viscosity reading over the 60 rpm reading. The closer that value themore similar the rheology response on the formulation. The Brookfieldviscosity response of the two polymers of this invention is around thatof the commercial polymer.

3. Pigments Floating Problems

Pigments were added to these paint formulations. The formulations werethen observed to detect pigment flotation issues. No pigment floatingissues was found.

4. Water Separation

TABLE 13 Water separation (mm) Polymer Room temperature 50° C. (60 days)Alcogum L-344 0 4 Example 7  0 1 Example 13 0 2

As shown in Table 13, all the polymers have no water separation problemsat room temperature. However, after 60 days at 50° C. the paints havingPolymers of this invention have less water separation compared to thepaint containing Alcogum L-344. This degree of water separation in thistest should have no impact on the paint performance as it can be blendedwell before application.

In summary, the performance of the polymers of this invention is similarto that of a commercial polymer in paint formulations.

Example 40

80 grams of a low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel (weight average molecular weight ofapproximately 300,000) was dispersed in 1675 grams of water containing1.6 grams of sodium sulfate in a 2 liter reactor equipped with stirrerand a heating mantle. The mixture was heated to 85 C while sparging withnitrogen. 0.338 grams of ferrous ammonium sulfate hexahydrate dissolvedin 21 grams of water and 8.3 grams of 35% hydrogen peroxide dissolved in53 grams of water was added. This was then held under nitrogen at 85° C.for 15 minutes to depolymerize the ethyl hydroxyethyl cellulose. Amonomer feed containing 97.2 grams of methacrylic acid, 120 grams ofn-butyl acrylate, 0.2 grams of diallyl phthalate and 21.43 grams of C₁₈alcohol with 20EO itaconate (associative monomer) was then added over 45minutes. Concurrently, an initiator solution containing 6.7 grams of 35%hydrogen peroxide dissolved in 42.8 grams of water was added over 110minutes. A nitrogen sparge is continued during these additions. Thereaction mixture was then cooked at 90° C. for an hour. The reactionproduct was allowed to cool overnight and separates out in to an aqueoustop phase and a bottom phase that is an opaque white paste which we termthe aqueous emulsion paste composition. This aqueous emulsion pastecomposition had 21.2% polymer with the rest being water. A sample ofthis aqueous emulsion paste was diluted to 2% polymer in water and thenneutralized with 50% NaOH to pH 8. The Brookfield viscosity of thissolution was 3970 cP at 10 rpm.

Example 41

80 grams of a low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel (weight average molecular weight ofapproximately 300,000) was dispersed in 1675 grams of water containing1.6 grams of sodium sulfate in a 2 liter reactor equipped with stirrerand a heating mantle. The mixture was heated to 85° C. while spargingwith nitrogen. 0.356 grams of ferrous ammonium sulfate hexahydratedissolved in 21 grams of water and 8.3 grams of 35% hydrogen peroxidedissolved in 53 grams of water was added. This was then held undernitrogen at 85° C. for 15 minutes to depolymerize the ethyl hydroxyethylcellulose. A monomer feed containing 97.2 grams of methacrylic acid, 154grams of n-butyl acrylate, 0.2 grams of diallyl phthalate and 21.43grams of C₁₈ alcohol with 20EO itaconate (associative monomer) was thenadded over 45 minutes. Concurrently, an initiator solution containing6.7 grams of 35% hydrogen peroxide dissolved in 42.8 grams of water wasadded over 110 minutes. A nitrogen sparge is continued during theseadditions. The reaction mixture was then cooked at 90° C. for an hour.The reaction product was allowed to cool overnight and separates out into an aqueous top phase and a bottom phase that is an opaque white pastewhich we term the aqueous emulsion paste composition. This aqueousemulsion paste composition had 23.9% polymer with the rest being water.A sample of this aqueous emulsion paste was diluted to 2% polymer inwater and then neutralized with 50% NaOH to pH 8. The Brookfieldviscosity of this solution was 4360 cP at 10 rpm.

Example 42

108 grams of a 85% Perfectamyl A4692 (oxidized potato starch from Avebewith a weight average molecular weight of 510,000) was dissolved in 1300grams of water in a 2 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 101.7 grams of methacrylicacid, 125.9 grams of n-butyl acrylate, 0.24 grams of diallyl phthalateand 22.4 grams of C₁₈ alcohol with 20EO itaconate (associative monomer)was prepared. 5 weight percent of this monomer mixture was added to thereactor. At the same time 0.27 grams of ammonium persulfate dissolved in19.8 grams of water was added. The reaction mixture was held at 85° C.for 15 minutes under nitrogen. The rest of the monomer was then addedover 90 minutes. Concurrently, an initiator solution containing 0.17grams of ammonium persulfate dissolved in 45 grams of water was addedover 120 minutes. A nitrogen sparge was continued during theseadditions. The reaction mixture was then cooked at 85° C. for an hour. Asolution of 0.17 grams of ammonium persulfate dissolved in 8 grams ofwater was added over 1 hour and then the reaction was held at 85° C. for30 minutes. The final product was a stable emulsion composition with 19%solids. A sample of this emulsion was diluted to 2% polymer in water andthen neutralized with 50% NaOH to pH 8. The Brookfield viscosity of thissolution was 2932 cP at 10 rpm.

Example 43

108 grams of a 85% Perfectamyl A4692 (oxidized potato starch from Avebewith a weight average molecular weight of 510,000) was dissolved in 1400grams of water in a 2 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 101.7 grams of methacrylicacid, 161 grams of n-butyl acrylate, 0.24 grams of diallyl phthalate and22.4 grams of C₁₈ alcohol with 20EO itaconate (associative monomer) wasprepared. 5 weight percent of this monomer mixture was added to thereactor. At the same time 0.27 grams of ammonium persulfate dissolved in19.8 grams of water was added. The reaction mixture was held at 85° C.for 15 minutes under nitrogen. The rest of the monomer was then addedover 90 minutes. Concurrently, an initiator solution containing 0.17grams of ammonium persulfate dissolved in 45 grams of water was addedover 120 minutes. A nitrogen sparge was continued during theseadditions. The reaction mixture was then cooked at 85° C. for an hour. Asolution of 0.17 grams of ammonium persulfate dissolved in 8 grams ofwater was added over 1 hour and then the reaction was held at 85° C. for30 minutes. The final product was a stable emulsion composition with19.2% solids. A sample of this emulsion was diluted to 2% polymer inwater and then neutralized with 50% NaOH to pH 8. The Brookfieldviscosity of this solution was 2760 cP at 10 rpm.

Example 44

33.6 grams of a low molecular weight ethyl hydroxyethyl cellulose (EHEC)Bermocoll® E230 from AkzoNobel (weight average molecular weight ofapproximately 300,000) was dispersed in 703.5 grams of water containing0.67 grams of sodium sulfate in a 1 liter reactor equipped with stirrerand a heating mantle. The mixture was heated to 85° C. while spargingwith nitrogen. 0.15 grams of ferrous ammonium sulfate hexahydratedissolved in 9 grams of water and 3.5 grams of 35% hydrogen peroxidedissolved in 22 grams of water was added. This was then held undernitrogen at 85° C. for 15 minutes to depolymerize the ethyl hydroxyethylcellulose. A monomer feed containing 66.6 grams of methacrylic acid,24.8 grams of ethyl acrylate, 0.1 grams of diallyl phthalate and 9 gramsof C₁₈ alcohol with 20EO itaconate (associative monomer) was then addedover 45 minutes. The ethyl acrylate was 20 weight percent of the totalmonomer. Concurrently, an initiator solution containing 2.8 grams of 35%hydrogen peroxide dissolved in 18 grams of water was added over 110minutes. A nitrogen sparge is continued during these additions. Thereaction mixture was then cooked at 90° C. for an hour. The reactionproduct was allowed to cool overnight and separates out in to an aqueoustop phase of 232 grams and a bottom aqueous emulsion paste compositionof 580 grams. This aqueous emulsion paste composition had 20% polymerwith the rest being water. A sample of this aqueous emulsion paste wasdiluted to 2% polymer in water and then neutralized with 50% NaOH to pH8. The Brookfield viscosity of this solution was 1720 cP at 10 rpm.

Example 45

33.6 grams of a low molecular weight starch (maltodextrin) Star Dri 5(from Tate and Lyle) was dissolved in 703.5 grams of water containing0.67 grams of sodium sulfate in a 1 liter reactor equipped with stirrerand a heating mantle. The mixture was heated to 85° C. while spargingwith nitrogen. 0.15 grams of ferrous ammonium sulfate hexahydratedissolved in 9 grams of water and 3.5 grams of 35% hydrogen peroxidedissolved in 22 grams of water was added. This was then held undernitrogen at 85° C. for 15 minutes. A monomer feed containing 73.8 gramsof methacrylic acid, 18.4 grams of ethyl acrylate, 0.1 grams of diallylphthalate and 9 grams of C₁₈ alcohol with 20EO itaconate (associativemonomer) was then added over 45 minutes. The ethyl acrylate was 20weight percent of the total monomer. Concurrently, an initiator solutioncontaining 2.8 grams of 35% hydrogen peroxide dissolved in 18 grams ofwater was added over 110 minutes. A nitrogen sparge is continued duringthese additions. The reaction mixture was then cooked at 85° C. for anhour. The reaction product was an emulsion with 14.3% solids. A sampleof this emulsion was diluted to 2% polymer in water and then neutralizedwith 50% NaOH to pH 8. The Brookfield viscosity of this solution was1832 cP at 10 rpm.

Example 46

33.6 grams of a low molecular weight starch (maltodextrin) Star Dri 5(from Tate and Lyle) was dissolved in 703.5 grams of water containing0.67 grams of sodium sulfate in a 1 liter reactor equipped with stirrerand a heating mantle. The mixture was heated to 85° C. while spargingwith nitrogen. 0.15 grams of ferrous ammonium sulfate hexahydratedissolved in 9 grams of water and 3.5 grams of 35% hydrogen peroxidedissolved in 22 grams of water was added. This was then held undernitrogen at 85° C. for 15 minutes. A monomer feed containing 79.9 gramsof methacrylic acid, 12.3 grams of ethyl acrylate, 0.1 grams of diallylphthalate and 9 grams of C₁₈ alcohol with 20EO itaconate (associativemonomer) was then added over 45 minutes. The ethyl acrylate was 12weight percent of the total monomer. Concurrently, an initiator solutioncontaining 2.8 grams of 35% hydrogen peroxide dissolved in 18 grams ofwater was added over 110 minutes. A nitrogen sparge is continued duringthese additions. The reaction mixture was then cooked at 85° C. for anhour. The reaction product was an emulsion with 14.3% solids. A sampleof this emulsion was diluted to 2% polymer in water and then neutralizedwith 50% NaOH to pH 8. The Brookfield viscosity of this solution was 206cP at 10 rpm. This example shows that a polymer containing justethylacrylate and methacrylic acid without an associative monomerrequires greater than 12 weight percent ethylacrylate based on theweight of the total monomer to give a viscosity of 500 cps at 10 rpm.This lower level of ethyl acrylate or hydrophobic monomer will change ifan associative monomer is added or the weight percent of thepolysaccharide or the type of polysaccharide is changed.

Example 47

65.6 grams of 85% Perfectamyl A4692 (oxidized potato starch from Avebewith a weight average molecular weight of 510,000) was dissolved in 692grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 48.3 grams of methacrylicacid, 109.5 grams of ethyl acrylate and 0.62 grams of trimethylolpropane triacrylate and was added over 90 minutes. Concurrently, aninitiator solution containing 0.66 grams of ammonium persulfatedissolved in 65 grams of water was added over 120 minutes. A nitrogensparge was continued during these additions. The reaction mixture wasthen cooked at 85° C. for 2 hours.

Example 48

54 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe) wasdissolved in 668 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 45.2grams of methacrylic acid, 21.1 grams of methyl acrylate, 0.12 grams ofdiallyl phthalate, 49.2 grams of n-butyl acrylate and 22.4 grams of aassociative monomer mixture which is 50% C₁₆₋₁₈ alcohol with 20EO, 25%methacrylic acid and 25% water was prepared. 5 weight percent of thismonomer mixture was added to the reactor. At the same time 0.41 grams ofammonium persulfate dissolved in 10 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N₂. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.26 grams of ammonium persulfate dissolved in 23grams of water was added over 120 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour. A solution of 0.24 grams of ammonium persulfatedissolved in 4 grams of water was added over 15 minutes and then thereaction was held at 85° C. for 30 minutes. The final product was anemulsion composition with 19.4% solids and was a stable emulsion forover 6 months.

Example 49

52.8 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 671 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 55.6grams of methacrylic acid, 0.12 grams of diallyl phthalate, 62.0 gramsof n-butyl acrylate and 21.8 grams of an associative monomer mixturewhich is 50% C₁₆₋₁₈ alcohol with 20EO, 25% methacrylic acid and 25%water was prepared. 5 weight percent of this monomer mixture was addedto the reactor. At the same time 0.37 grams of ammonium persulfatedissolved in 10 grams of water was added. The reaction mixture was heldat 85° C. for 15 minutes under N₂. The rest of the monomer was thenadded over 90 minutes. Concurrently, an initiator solution containing0.25 grams of ammonium persulfate dissolved in 23 grams of water wasadded over 120 minutes. A nitrogen sparge was continued during theseadditions. The reaction mixture was then cooked at 85° C. for an hour. Asolution of 0.24 grams of ammonium persulfate dissolved in 4 grams ofwater was added over 15 minutes and then the reaction was held at 85° C.for 30 minutes. The final product was an emulsion composition with 19.4%solids and was a stable emulsion for over 6 months.

Example 50

52.9 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 631 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 55.6grams of methacrylic acid, 20.7 grams of methyl acrylate, 0.12 grams ofdiallyl phthalate, 31.2 grams of n-butyl acrylate and 21.8 grams of anassociative monomer mixture which is 50% C₁₆₋₁₈ alcohol with 20EO, 25%methacrylic acid and 25% water was prepared. 5 weight percent of thismonomer mixture was added to the reactor. At the same time 0.40 grams ofammonium persulfate dissolved in 10 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N₂. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.25 grams of ammonium persulfate dissolved in 23grams of water was added over 120 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour. A solution of 0.24 grams of ammonium persulfatedissolved in 4 grams of water was added over 15 minutes and then thereaction was held at 85° C. for 30 minutes. The final product was anemulsion composition with 19.2% solids and was a stable emulsion forover 6 months.

Example 51

56.9 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 684 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 53.5grams of methacrylic acid, 66.3 grams of ethyl acrylate and 0.126 gramsof diallyl phthalate was prepared. 5 weight percent of this monomermixture was added to the reactor. At the same time 0.14 grams ofammonium persulfate dissolved in 10 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N₂. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.084 grams of ammonium persulfate dissolved in 24grams of water was added over 120 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour. A solution of 0.084 grams of ammonium persulfatedissolved in 4 grams of water was added over 15 minutes and then thereaction was held at 85° C. for 30 minutes. The final product was anemulsion composition with 18.1% solids and was a stable emulsion forover 6 months.

Example 52

65.4 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 665 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 61.5grams of methacrylic acid, 65.5 grams of methyl acrylate and 0.145 gramsof diallyl phthalate was prepared. 5 weight percent of this monomermixture was added to the reactor. At the same time 0.16 grams ofammonium persulfate dissolved in 12 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N₂. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.1 grams of ammonium persulfate dissolved in 27.7grams of water was added over 120 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour. A solution of 0.1 grams of ammonium persulfatedissolved in 4 grams of water was added over 15 minutes and then thereaction was held at 85° C. for 30 minutes. The final product was anemulsion composition with 19.9% solids and was a stable emulsion forover 6 months.

Example 52

56.2 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 676 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 52.9grams of methacrylic acid, 56.3 grams of methyl acrylate, 11.7 grams ofC₁₈ alcohol with 20EO itaconate (associative monomer), and 0.125 gramsof diallyl phthalate was prepared. 5 weight percent of this monomermixture was added to the reactor. At the same time 0.14 grams ofammonium persulfate dissolved in 10 grams of water was added. Thereaction mixture was held at 85° C. for 15 minutes under N₂. The rest ofthe monomer was then added over 90 minutes. Concurrently, an initiatorsolution containing 0.89 grams of ammonium persulfate dissolved in 24grams of water was added over 120 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour. A solution of 0.08 grams of ammonium persulfatedissolved in 4 grams of water was added over 15 minutes and then thereaction was held at 85° C. for 30 minutes. The final product was anemulsion composition with 18.2% solids and was a stable emulsion forover 6 months.

Example 53

55.7 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 680 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 53.5grams of methacrylic acid, 66.3 grams of ethyl acrylate and 0.126 gramsof diallyl phthalate was prepared. An initiator solution containing 0.58grams of ammonium persulfate dissolved in 52 grams of water wasprepared. 5 weight percent of the monomer mixture above was added to thereactor and held for 15 minutes. 9 weight percent of the initiatormixture above was added to the reactor and held for 15 minutes. The restof the monomer was then added over 90 minutes. Concurrently the rest ofthe initiator solution was added over 90 minutes. A nitrogen sparge wascontinued during these additions. The reaction mixture was then cookedat 85° C. for an hour and then 2 hours at 70° C. The final product wasan emulsion composition with 19.8% solids and was a stable emulsion forover 6 months.

Example 54

55.7 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 680 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 50.7grams of methacrylic acid, 87.6 grams of ethyl acrylate and 0.55 gramsof trimethylol propyl triacrylate (TMPTA) was prepared. An initiatorsolution containing 0.58 grams of ammonium persulfate dissolved in 52grams of water was prepared. The monomer solution was then added over 90minutes. Concurrently the initiator solution was added over 90 minutes.A nitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for an hour and then 2 hours at 70° C.The final product was an emulsion composition with 19.8% solids and wasa stable emulsion for over 6 months.

Example 55 Evaluation of Samples in Examples 47 to 54 in ShampooFormulation

200 grams of typical shampoo base was prepared by adding 59.58 grams ofDeionized water to a 250 ml beaker. A small 1½ inch jiffy mixer bladewas inserted into the beaker and attached to an overhead mixer. Thebatch was allowed to mix with a vortex extending to the middle of thebeaker. Then 24.30 grams (3% active polymer) of Examples 1 to 8 wasadded and allowed to mix until uniform. This was followed by adding62.74 grams of Sodium Laureth Sulfate (25.2% active Standapol ES-2 fromCognis Corporation, FairField, N.J.). This was allowed to mix until itwas homogenous. Then 27.58 grams of Sodium Lauryl sulfate (Witconate WACLA, Akzo Nobel, Houston, Tex.) was added and mixed until homogenous.Then 22.80 grams of Cocamidoproply Betaine (Crodateric CAB 30, CrodaInc, Edison, N.J.) was added an allowed to mix until homogenous. Then1.0 grams of DMDM Hydantoin and IodopropynylButylcarbamate Glydant Plus(Liquid), Lonza Corp Allendale, N.J.) was added and the batch was mixeduntil homogenous. The pH was then adjusted to 6.5+/−0.25 using 25%sodium hydroxide (Fisher Scientific, Fairlawn, N.J.) as needed. Once thebatch was uniform 2 grams of cosmetic beads, Floraspheres JoJoba MDSbeads (Floratech, Chandler, Ariz.) were gently folded into the batchuntil they were evenly distributed throughout the batch.

To test the suspension properties of the cosmetic beads, the shampooformulations were placed in a 45° C. oven and the dispersion of thebeads was visually monitored for migration of the beads. The results areshown in Table 14. Any sample that showed migration of the beads wasdeemed a failure.

TABLE 14 Polymer of Example 45° C. Suspension Results None Did notsuspend Example 47 Suspended for 90+ days  Example 48 Suspended for 120+days Example 49 Suspended for 90+ days  Example 50 Suspended for 120+days Example 51 Suspended for 120+ days Example 52 Suspended for 120+days Example 53 Suspended for 120+ days Example 54 Suspended for 120+days

Example 56

55.7 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 680 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 50.7grams of methacrylic acid, 87.6 grams of ethyl acrylate and 1.06 gramsof polyethylene glycol diacrylate was prepared. An initiator solutioncontaining 0.58 grams of ammonium persulfate dissolved in 52 grams ofwater was prepared. The monomer solution was then added over 90 minutes.Concurrently the initiator solution was added over 90 minutes. Anitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for an hour and then 2 hours at 70° C.The final product was an emulsion composition with 19.5% solids and wasa stable emulsion for over 6 months.

Example 57

66.9 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 680 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 47.3grams of methacrylic acid, 81.2 grams of ethyl acrylate and 0.51 gramsof trimethylol propyl triacrylate (TMPTA) was prepared. An initiatorsolution containing 0.58 grams of ammonium persulfate dissolved in 52grams of water was prepared. The monomer solution was then added over 90minutes. Concurrently the initiator solution was added over 90 minutes.A nitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for an hour and then 2 hours at 70° C.The final product was an emulsion composition with 19.7% solids and wasa stable emulsion for over 6 months.

Example 58

89.2 grams of 85% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 675 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 40.6grams of methacrylic acid, 70.1 grams of ethyl acrylate and 0.44 gramsof trimethylol propyl triacrylate (TMPTA) was prepared. An initiatorsolution containing 0.58 grams of ammonium persulfate dissolved in 52grams of water was prepared. The monomer solution was then added over 90minutes. Concurrently the initiator solution was added over 90 minutes.A nitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for an hour and then 2 hours at 70° C.The final product was an emulsion composition with 19.6% solids and wasa stable emulsion for over 6 months.

Example 59

111.5 grams of 83% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 671.5 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 33.8grams of methacrylic acid, 58.4 grams of ethyl acrylate and 0.37 gramsof trimethylol propyl triacrylate (TMPTA) was prepared. An initiatorsolution containing 0.58 grams of ammonium persulfate dissolved in 52.1grams of water was prepared. The monomer solution was then added over 90minutes. Concurrently the initiator solution was added over 90 minutes.A nitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for 2 hours. The final product was anemulsion composition with 19.9% solids.

Example 60

57.2 grams of 80.9% PR1004B (oxidized potato starch from Avebe that is ahigher molecular weight than Perfectamyl 4692) was dissolved in 675grams of water in a 1 liter reactor equipped with stirrer and a heatingmantle. The mixture was heated to 85° C. while sparging with nitrogenfor one hour. A monomer solution containing 50.7 grams of methacrylicacid, 87.6 grams of ethyl acrylate and 0.55 grams of trimethylol propyltriacrylate (TMPTA) was prepared. An initiator solution containing 0.58grams of ammonium persulfate dissolved in 52 grams of water wasprepared. The monomer solution was then added over 90 minutes.Concurrently the initiator solution was added over 90 minutes. Anitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for an hour and then 2 hours at 70° C.The final product was an emulsion composition with 19.4% solids.

Example 61

The polymer from examples 56 to 60 were evaluated in a shampooformulation as described in Example 55. The results of this evaluationare detailed in Table 15 below.

TABLE 15 Polymer of Example 45° C. Suspension Results None Did notsuspend Example 56 Suspended for 10+ days Example 57 Suspended for 10+days Example 58 Suspended for 10+ days Example 59 Suspended for 10+ daysExample 60 Suspended for 10+ days

Example 62

89.2 grams of 83% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 675.3 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 40.6grams of methacrylic acid, 70.1 grams of ethyl acrylate and 0.44 gramsof trimethylol propyl triacrylate (TMPTA) was prepared. An initiatorsolution containing 0.58 grams of ammonium persulfate dissolved in 52.1grams of water was prepared. The monomer solution was then added over 90minutes. Concurrently the initiator solution was added over 90 minutes.A nitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for an hour and then 2 hours at 70° C.The final product was an emulsion composition with 19.9% solids.

Example 63

111.5 grams of 83% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 671.5 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 33.8grams of methacrylic acid, 58.4 grams of ethyl acrylate and 0.37 gramsof trimethylol propyl triacrylate (TMPTA) was prepared. An initiatorsolution containing 0.58 grams of ammonium persulfate dissolved in 52.1grams of water was prepared. The monomer solution was then added over 90minutes. Concurrently the initiator solution was added over 90 minutes.A nitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for two hours. The final product wasan emulsion composition with 19.9% solids.

Example 64

62.4 grams of 80.9% PR1004B (a higher molecular weight oxidized potatostarch from Avebe) was dissolved in 742.3 grams of water in a 1 literreactor equipped with stirrer and a heating mantle. The mixture washeated to 85° C. while sparging with nitrogen for one hour. A monomersolution containing 55.3 grams of methacrylic acid, 95.5 grams of ethylacrylate and 0.60 grams of trimethylol propyl triacrylate (TMPTA) wasprepared. An initiator solution containing 0.64 grams of ammoniumpersulfate dissolved in 56.8 grams of water was prepared. The monomersolution was then added over 90 minutes. Concurrently the initiatorsolution was added over 90 minutes. A nitrogen sparge was continuedduring these additions. The reaction mixture was then cooked at 85° C.for two hours. The final product was an emulsion composition with 19.5%solids.

Example 65

74.9 grams of 80.9% PR1004B (a higher molecular weight oxidized potatostarch from Avebe) was dissolved in 742.3 grams of water in a 1 literreactor equipped with stirrer and a heating mantle. The mixture washeated to 85° C. while sparging with nitrogen for one hour. A monomersolution containing 51.6 grams of methacrylic acid, 89.1 grams of ethylacrylate and 0.51 grams of trimethylol propyl triacrylate (TMPTA) wasprepared. An initiator solution containing 0.64 grams of ammoniumpersulfate dissolved in 56.8 grams of water was prepared. The monomersolution was then added over 90 minutes. Concurrently the initiatorsolution was added over 90 minutes. A nitrogen sparge was continuedduring these additions. The reaction mixture was then cooked at 85° C.for two hours. The final product was an emulsion composition with 19.4%solids.

Example 66

55.8 grams of 83% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 681 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 50.7grams of methacrylic acid, 87.6 grams of ethyl acrylate and 1.06 gramsof polyethylene glycol 400 diacrylate was prepared. An initiatorsolution containing 0.58 grams of ammonium persulfate dissolved in 52.1grams of water was prepared. The monomer solution was then added over 90minutes. Concurrently the initiator solution was added over 90 minutes.A nitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for an hour and then 2 hours at 70° C.The final product was an emulsion composition with 19.9% solids.

Example 67

60.8 grams of 83% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 742.3 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 55.3grams of methacrylic acid, 95.6 grams of ethyl acrylate and 0.54 gramsof pentaerythritol tetraacrylate was prepared. An initiator solutioncontaining 0.64 grams of ammonium persulfate dissolved in 56.8 grams ofwater was prepared. The monomer solution was then added over 90 minutes.Concurrently the initiator solution was added over 90 minutes. Anitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for two hours. The final product wasan emulsion composition with 19.3% solids.

Example 68

60.8 grams of 83% Perfectamyl 4692 (oxidized potato starch from Avebe)was dissolved in 742.3 grams of water in a 1 liter reactor equipped withstirrer and a heating mantle. The mixture was heated to 85° C. whilesparging with nitrogen for one hour. A monomer solution containing 55.3grams of methacrylic acid, 95.6 grams of ethyl acrylate and 0.43 gramsof dipentaerythritol pentaacrylate was prepared. An initiator solutioncontaining 0.64 grams of ammonium persulfate dissolved in 56.8 grams ofwater was prepared. The monomer solution was then added over 90 minutes.Concurrently the initiator solution was added over 90 minutes. Anitrogen sparge was continued during these additions. The reactionmixture was then cooked at 85° C. for two hours. The final product wasan emulsion composition with 19.8% solids.

Example 69

73.3 grams of 80.9% PR1004B (a higher molecular weight oxidized potatostarch from Avebe) was dissolved in 800 grams of water in a 1 literreactor equipped with stirrer and a heating mantle. The mixture washeated to 85° C. while sparging with nitrogen for one hour. A monomersolution containing 32.5 grams of methacrylic acid, 56.1 grams of ethylacrylate and 0.35 grams of trimethylol propyl triacrylate (TMPTA) wasprepared. An initiator solution containing 0.47 grams of ammoniumpersulfate dissolved in 41.7 grams of water was prepared. The monomersolution was then added over 90 minutes. Concurrently the initiatorsolution was added over 90 minutes. A nitrogen sparge was continuedduring these additions. The reaction mixture was then cooked at 85° C.for two hours. The final product was an emulsion composition with 14.3%solids.

Example 70

91.6 grams of 80.9% PR1004B (a higher molecular weight oxidized potatostarch from Avebe) was dissolved in 800 grams of water in a 1 literreactor equipped with stirrer and a heating mantle. The mixture washeated to 85° C. while sparging with nitrogen for one hour. A monomersolution containing 27.0 grams of methacrylic acid, 46.7 grams of ethylacrylate and 0.29 grams of trimethylol propyl triacrylate (TMPTA) wasprepared. An initiator solution containing 0.47 grams of ammoniumpersulfate dissolved in 41.7 grams of water was prepared. The monomersolution was then added over 90 minutes. Concurrently the initiatorsolution was added over 90 minutes. A nitrogen sparge was continuedduring these additions. The reaction mixture was then cooked at 85° C.for two hours. The final product was an emulsion composition with 14.4%solids.

Example 71

50.8 grams of a low molecular weight Carboxymethyl cellulose (CMC)(Finnfix 2 from CP Kelco) was dissolved in 686 grams of water in a 1liter reactor equipped with stirrer and a heating mantle. The mixturewas heated to 85° C. while sparging with nitrogen for one hour. Amonomer solution containing 50.7 grams of methacrylic acid, 87.6 gramsof ethyl acrylate and 0.55 grams of trimethylol propyl triacrylate(TMPTA) was prepared. An initiator solution containing 0.58 grams ofammonium persulfate dissolved in 52 grams of water was prepared. 5weight percent of the monomer mixture above was added to the reactor andheld for 15 minutes. 9 weight percent of the initiator mixture above wasadded to the reactor and held for 15 minutes. The rest of the monomerwas then added over 90 minutes. Concurrently the rest of the initiatorsolution was added over 90 minutes. A nitrogen sparge was continuedduring these additions. The reaction mixture was then cooked at 85° C.for an hour and then 2 hours at 70° C. The final product was an emulsioncomposition with 19.8% solids.

Example 72

103 grams of a crosslinked starch ThermFlo (available from Ingredion)was mixed with 706 grams of water in a reactor equipped with stirrer anda heating mantle. The mixture was heated to 95° C. A solution of 10grams of 35% hydrogen peroxide in 250 grams of water was added and thereaction mixture was held at 95° C. for 1 hour. The viscosity droppednoticeably in this time. The reaction temperature was dropped to 85° C.and was sparged with nitrogen for one hour. A monomer solutioncontaining containing 101.7 grams of methacrylic acid, 125.9 grams ofethyl acrylate, 0.25 grams of diallylphthalate and 22.5 grams of C₁₆alcohol with 20 EO itaconate (associative monomer) was prepared. 5weight percent of the monomer mixture above was added to the reactor.Concurrently an initiator solution containing 0.27 grams of ammoniumpersulfate dissolved in 20 grams of water was added with the monomersolution and held for 15 minutes. The rest of the monomer was then addedover 90 minutes. Concurrently an initiator solution containing 0.17grams of ammonium persulfate dissolved in 45 grams of water was addedwith the monomer solution. A nitrogen sparge was continued during theseadditions. The reaction mixture was then cooked at 85° C. for an hour.

Example 73

91.6 grams of 80.9% octenyl succinic anhydride with a water fluidity(WF) of 80 was dissolved in 800 grams of water in a reactor equippedwith stirrer and a heating mantle. The mixture was heated to 85° C.while sparging with nitrogen for one hour. A monomer solution containing27.0 grams of methacrylic acid, 46.7 grams of ethyl acrylate and 0.29grams of trimethylol propyl triacrylate (TMPTA) was prepared. Aninitiator solution containing 0.47 grams of ammonium persulfatedissolved in 41.7 grams of water was prepared. The monomer solution wasthen added over 90 minutes. Concurrently the initiator solution wasadded over 90 minutes. A nitrogen sparge was continued during theseadditions. The reaction mixture was then cooked at 85° C. for two hours.The final product was an emulsion composition with 14.4% solids.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention.

While particular embodiments of the present invention have beenillustrated and described herein, the invention is not intended to belimited to the details shown. Rather, various modifications may be madein the details within the range and scope of equivalents of the claimsand without departing from the spirit and scope of the invention.

We claim:
 1. A polysaccharide alkali swellable rheology modifiercomprising an emulsion polymer comprising at least one polysaccharideportion and at least one synthetic portion, said polysaccharide alkaliswellable rheology modifier being obtainable by emulsion polymerizing atleast one polysaccharide with at least one anionic ethylenicallyunsaturated monomer and at least one nonionic ethylenically unsaturatedmonomer in the presence of an initiating system, the emulsion polymerfurther comprising at least one associative monomer that is anethylenically unsaturated monomer containing a hydrophobe and a spacermoiety that spaces the hydrophobe from the backbone of the polymer,wherein the minimum weight of anionic ethylenically unsaturated monomeris about 15 weight percent or more of the total monomer added to thepolymerization process, wherein at least one of the at least onenonionic ethylenically unsaturated monomers is a hydrophobicethylenically unsaturated monomer present in an amount effective to forman emulsion, and wherein when the polysaccharide portion is obtainedfrom cellulose or a cellulose derivative, the cellulose or cellulosederivative has about 0.1% or greater solubility in water at 25° C. 2.The rheology modifier of claim 1 wherein the polysaccharide portion isobtained from a starch or a starch derivative or a cellulose or acellulose derivative.
 3. The rheology modifier of claim 1 wherein thepolysaccharide portion is obtained from a starch or starch derivativeselected from the group consisting of thermally treated starch,mechanically treated starch, oxidatively degraded starch, hydrolyticallydegraded starch, enzymatically degraded starch, chemically modifiedstarches and combinations thereof.
 4. The rheology modifier of claim 3wherein the starch derivative is selected from the group consisting ofmaltodextrin, dextrin, pyrodextrin, oxidized starch, cyclodextrin,substituted cyclodextrins, higher molecular weight starch, hydrogenatedstarch hydrolyslates and combinations thereof.
 5. The rheology modifierof claim 1 wherein the polysaccharide portion is obtained from acellulose or cellulose derivative selected from the group consisting ofcarboxymethyl cellulose (CMC), hydroxethyl cellulose (HEC),carboxymethyl hydroxethyl cellulose (CMHEC), hydroxypropyl cellulose(HPC), ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethylcellulose (MEHEC), and hydrophobically modified ethyl hydroxy ethylcelluloses (HM-EHEC) and combinations thereof.
 6. The rheology modifierof claim 1 wherein the anionic ethylenically unsaturated monomer isselected from the group consisting of acrylic acid, maleic acid,methacrylic acid, itaconic acid, 2-acrylamido-2-methyl propane sulfonicacid and mixtures thereof.
 7. The rheology modifier of claim 1 whereinthe hydrophobic ethylenically unsaturated monomer is selected from thegroup consisting of ethyl (meth)acrylate, methyl (meth)acrylate,2-ethylhexyl acrylate, butyl (meth)acrylate, vinyl acetate, tertiarybutyl acrylamide and combinations thereof.
 8. The rheology modifier ofclaim 1 wherein the hydrophobic ethylenically unsaturated monomer has awater solubility of about less than 3 grams per 100 mls of water at 25°C.
 9. The rheology modifier of claim 1 wherein the hydrophobe with thespacer moiety is selected from the group consisting of alcoholethoxylates, alkylphenoxy ethoxylates, propoxylated/butoxylatedethoxylates and ethoxylated silicones.
 10. The rheology modifier ofclaim 1 wherein the minimum weight percent of the polysaccharide portionis about 5% of the polysaccharide alkali swellable rheology modifier andthe maximum weight percent of the polysaccharide portion is about 90% ofthe polysaccharide alkali swellable rheology modifier.
 11. The rheologymodifier of claim 1 wherein the rheology modifier has a weight averagemolecular weight of about 5,000,000 or less.
 12. A method of making apolysaccharide alkali swellable rheology modifier comprising: emulsionpolymerizing a polysaccharide with at least one anionic ethylenicallyunsaturated monomer, and at least one nonionic ethylenically unsaturatedmonomer in the presence of an initiating system, wherein at least one ofthe at least one nonionic ethylenically unsaturated monomers is ahydrophobic ethylenically unsaturated monomer and is present in anamount effective to form an emulsion, and wherein the hydrophobicethylenically unsaturated monomer is present an amount effective to forman emulsion, wherein the minimum weight of anionic ethylenicallyunsaturated monomer is about 15 weight percent or more of the totalmonomer added to the polymerization process, and wherein the emulsionpolymerization step is conducted substantially free of surfactant. 13.The method of claim 12 wherein the polysaccharide is depolymerizedbefore or during the polymerizing step.
 14. A composition comprising therheology modifier according to claim 1 wherein the composition isselected from the group consisting of a personal care composition, afabric and cleaning composition, an oil field composition, anagricultural composition, a paint composition and a coating composition.15. A polysaccharide alkali swellable rheology modifier comprising anemulsion polymer comprising at least one polysaccharide portion and atleast one synthetic portion, said polysaccharide alkali swellablerheology modifier being obtainable by emulsion polymerizing at least onepolysaccharide with at least one anionic ethylenically unsaturatedmonomer and at least one nonionic ethylenically unsaturated monomer inthe presence of an initiating system, wherein the minimum weight ofanionic ethylenically unsaturated monomer is about 15 weight percent ormore of the total monomer added to the polymerization process, whereinat least one of the at least one nonionic ethylenically unsaturatedmonomers is a hydrophobic ethylenically unsaturated monomer present inan amount effective to form an emulsion, wherein when the Polysaccharideportion is obtained from cellulose or a cellulose derivative, thecellulose or cellulose derivative has about 0.1% or greater solubilityin water at 25° C., and wherein the emulsion polymer is substantiallyfree of surfactant.
 16. A stable emulsion system comprising thepolysaccharide alkali swellable rheology modifier of claim 1, unreactedpolysaccharide and water, the system comprising at least 10 wt % solids.17. A stable emulsion system comprising the polysaccharide alkaliswellable rheology modifier of claim 15, unreacted polysaccharide andwater, the system comprising at least 10 wt % solids.